Hydrocarbon-terminated polyether-polyamide block copolymers and uses thereof

ABSTRACT

A composition comprising (a) a resin composition comprising a block copolymer of the formula hydrocarbon-polyether-polyamide-polyether-hydrocarbon; and (b) a polar liquid. The block copolymer may be prepared by a process comprising reacting together reactants comprising dimer acid, diamine, and a polyether having termination at one end selected from amine, hydroxyl and carboxyl, and termination at another end selected from hydrocarbons. The polar liquid may be one or more of an aromatic liquid, a polar aprotic liquid, a ketone-containing liquid, an ester-containing liquid, an ether-containing liquid, an amide-containing liquid and a sulfoxide-containing liquid. The composition may be a gel at room temperature.

This application is a Continuation of Ser. No. 10/142,664, filed May 8,2002 now U.S. Pat. No. 6,870,011, which was a CIP of Ser. No.09/769,081, filed Jan. 24, 2001 now U.S. Pat. No. 6,399,713.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention generally relates to organic resins, more particularly toresins having an internal structure comprised of polyamide andpolyether, and terminal structure comprised of hydrocarbon. Theinvention also relates to the preparation of these resins, and their useas, for example, gelling agents for liquids.

2. Description of the Related Art

In many commercially important compositions, the consistency of theproduct is critical to its commercial success. One example is personalcare products, which generally contain one or more active ingredientswithin a carrier formulation. While the active ingredient(s) determinethe ultimate performance properties of the product, the carrierformulation is equally critical to the commercial success of the productin that it largely determines the consistency of the product. Therheology of the carrier (also referred to as the “base”) largelydetermines the flow properties of the product, and the flow propertieslargely determine the manner in which the consumer will apply or use theproduct.

For example, aluminum chlorohydrate, aluminum-zirconiumtetrachlorohydrate, aluminum-zirconium polychlorohydrate complexed withglycine, and aluminum-zirconium complexed with any of trichlorohydrate,octachlorohydrate, and sesquichlorohydrate are metal salts that arecommonly used as active ingredients in deodorant and antiperspirantproducts. Consumers have shown a preference for applying deodorant froma stick form. Thus, the carrier in a stick-form deodorant must be arelatively hard substance, and waxy fatty alcohol such as stearylalcohol has often been used as the carrier in these products. As anotherexample, the active ingredient in a lipstick is the colorant. A lipstickshould not be as hard as a stick deodorant, but of course must maintainits shape when undisturbed at room temperature. A blend of wax and oilis known to provide a consistency that is well suited as a carrier for alipstick. As a final example, shampoo desirably has a viscosity greaterthan water, and when the active ingredient(s) in a shampoo does not havea sufficiently high viscosity, a somewhat viscous carrier material isdesirably included in the shampoo formulation.

From the above examples, it is seen that formulators of personal careproducts depend upon the availability of materials having variousrheological properties, in order to formulate a successful personal careproduct. Materials which have a gel-like character, in that theymaintain their shape when undisturbed but flow upon being rubbed, areoften desired for personal care products.

Transparent (i.e., clear) carriers are desired by formulators whodevelop a personal care product wherein colorant is an activeingredient, because a transparent carrier (as opposed to an opaquecarrier) will minimally, if at all, interfere with the appearance of thecolorant. In recent years, consumers have demonstrated an increasingpreference for transparent and colorless personal care products such asdeodorants and shampoos. There is thus an increasing demand fortransparent materials that can provide the rheological properties neededfor various personal care products, and particularly which can impartgel-like character to a formulation.

Polyamide resin prepared from polymerized fatty acid and diamine isreported to function as a gellant in formulations developed for personalcare products. For example, U.S. Pat. No. 3,148,125 is directed to aclear lipstick carrier composition formed from polyamide resincompounded with a lower aliphatic alcohol and a so-called “polyamidesolvent.” Likewise, U.S. Pat. No. 5,500,209 is directed to forming a gelor stick deodorant, where the composition contains polyamide gellingagent and a solvent system including monohydric or polyhydric alcohols.Thus, the prior art recognizes to blend certain polyamides withalcohols, to thereby form a gel.

Polar solvents, e.g., ether- and hydroxyl-containing materials which areliquid at or slightly above room temperature, are desirably included inpersonal care formulations because they are often benign, allow dilutionwith at least some water, dissolve a wide range of active and inactiveformulation ingredients and are relatively inexpensive. Polar solventsare also available in a wide variety of viscosities and grades. However,these solvents typically do not have the rheological properties that aredesired in a carrier, e.g., they do not naturally exhibit gel-likecharacter. Furthermore, gellants for this type of solvent are uncommonand often unavailable.

Accordingly, there is a need in the art for materials that can becombined with solvents, and particularly polar solvents, to afford atransparent material that has gel-like character. The present inventionprovides this and related advantages as described herein.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the present invention provides a composition comprising(a) a resin composition comprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon; and (b) a polarliquid. For example, the composition may include a block copolymerwherein the polyether block comprises the formula

R²—O

where R² is a hydrocarbon; the polyamide block comprises the formula

where R³ is a hydrocarbon and R⁴ is selected from hydrocarbons andpolyethers; and the hydrocarbon termini are independently selected fromC₁₋₂₂ hydrocarbon radicals. As another example, the composition mayinclude a block copolymer of the formula

wherein, independently at each occurrence, R¹ is a C₁₋₂₂ hydrocarbonradical; R² is a C₂₋₆ hydrocarbon diradical; and R³ is a C₂₋₅₂hydrocarbon diradical, where at least 50% of the R³ diradicals have atleast 34 carbons; R⁴ is selected from C₂₋₃₆ hydrocarbon diradicals andC₄-C₁₀₀ polyether diradicals; Z is selected from O and NH; x is aninteger from 2 to 100; y is an integer from 1 to 10; and z is an integerfrom 2 to 100. As another example, the composition may include a blockcopolymer of the formula

wherein, independently at each occurrence, R¹ is a C₁₋₂₂ hydrocarbonradical; R² is a C₂₋₆ hydrocarbon diradical; R³ is a C₂₋₅₂ hydrocarbondiradical, where at least 50% of the R³ diradicals are 1,4-cyclohexanediradical; R⁴ is selected from C₂₋₃₆ hydrocarbon diradicals and C₄-C₁₀₀polyether diradicals; Z is selected from O and NH; x is an integer from2 to 100; y is an integer from 1 to 10; and z is an integer from 2 to100. When 1,4-CHDA contributes more than about 50% of the acidequivalents, then it is preferred that few or none of the R⁴ groups haveless than 6 carbons. As another example, the resin composition maycomprise a hydrocarbon-polyether-polyamide-polyether-hydrocarbon blockcopolymer of the formula

wherein, independently at each occurrence, R¹ is a C₁₋₈ hydrocarbonradical; R² is a C₂₋₄ hydrocarbon diradical; R³ is a C₂₋₅₂ hydrocarbondiradical, where at least 50% of the R³ diradicals are derived fromdimer acid; R⁴ is selected from C₂₋₈ hydrocarbon diradicals andpolyether diradicals of the formula —(R¹¹—O)_(g)—R¹¹— wherein R¹¹ is aC₂-C₆ hydrocarbon diradical independently selected at each occurrenceand g is an integer from 2 to 100; Z is selected from O and NH; x is aninteger from 2 to 100; y is an integer equal to 1 or more that providesa copolymer molecular weight of 2,000 to 50,000, and z is an integerfrom 2 to 100. As another example, the composition may include a blockcopolymer prepared by a process comprising reacting together reactantscomprising dimer acid, diamine, and a polyether having termination atone end selected from amine, hydroxyl and carboxyl, and termination atanother end selected from hydrocarbons. As another example, thecomposition may include a block copolymer prepared by a processcomprising reacting together reactants comprising diamine,cyclohexane-dicarboxylic acid, and a polyether having termination at oneend selected from amine, hydroxyl and carboxyl, and termination atanother end selected from hydrocarbon. As another example, thehydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymermay be prepared by a process comprising reacting together reactantscomprising dimer acid, polyetherdiamine, alkylenediamine, and amonofunctional polyether having both hydrocarbon termination andtermination selected from amine, hydroxyl and carboxyl, under reactionconditions that form the block copolymer.

In each of the compositions identified above, and identified elsewhereherein, in one aspect the polar liquid is one or more of an aromaticliquid, a polar aprotic liquid, a ketone-containing liquid, anester-containing liquid, an ether-containing liquid, an amide-containingliquid and a sulfoxide-containing liquid. The composition may be aliquid, which will typically be the case at elevated temperatures. Thecomposition may alternatively be a gel, which will typically be the caseat room temperature. Even when the composition is in the gel state, thepolar liquid of the composition will be deemed to be a “liquid”, i.e., afluid, even if the composition does not demonstrate syneresis. In fact,the composition preferably does not demonstrate syneresis. The polarliquid within the composition of the present invention will beconsidered to be a “liquid” for purposes of the present invention, eventhough the composition demonstrates a gel consistency.

In one aspect, the polar liquid is an ester-containing liquid having aformula selected from R⁶—CO₂—R⁶ and R⁶—CO₂—R⁷—CO₂—R⁶ wherein R⁶ and R⁷are organic moieties having 1-12 carbons, where two R⁶ moieties in aliquid may be joined together to provide a lactone, and a R⁶ and R⁷moiety in a liquid may be joined together to form a lactone. Forexample, R⁶ may be selected from C₁-C₁₂ alkyl, C₁-C₁₂hydroxy-substituted alkyl, C₁-C₁₂ alkoxy-substituted C₁-C₁₂ alkyl,C₆-C₁₂ aryl-substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₁-C₁₂hydroxyalkenyl, C₁-C₁₂ alkoxy-substituted C₁-C₁₂ alkenyl, C₆-C₁₂ aryl,C₁-C₁₂ alkyl-substituted C₆-C₁₂ aryl, C₆-C₁₂ hydroxy-substituted aryl,C₆-C₁₂ alkoxy-substituted C₆-C₁₂ aryl; and R⁷ may be selected fromC₁-C₁₂ alkylene, C₁-C₁₂ hydroxy-substituted alkylene, C₂-C₁₂ alkenylene,C₆-C₁₂ arylene, C₆-C₁₂ hydroxy-substituted arylene, C₁-C₁₂alkoxy-substituted C₆-C₁₂ arylene. As another example, theester-containing liquid may be selected from the group consisting ofethyl lactate, butyl propionate, dibutyl adipate, ethoxyethylpropionate, butyl acrylate, vinyl propionate, butyl acetate, dibutylsebacate, diethylphthalate, vinyl acetate, methyl methacrylate, ethylacetate, ethyl hexyl acetate, and gamma-butyrolactone.

In another aspect, the polar liquid is an aromatic liquid. For example,the aromatic liquid may be selected from the group consisting ofbenzene, toluene, o-xylene, m-xylene, p-xylene, styrene, alpha-methylstyrene, (C₁-C₁₈ alkyl)-benzoate, (C₁-C₁₈ alkyl)salicylate, and (C₁-C₁₂alkyl)(C₁-C₁₂ alkyl)phthalate.

In another aspect, the polar liquid is a polar aprotic liquid. Forexample, the polar aprotic liquid may be selected from the groupconsisting of N-methylpyrrolidinone, propylene carbonate,tetrahydrofuran, dimethyl sulfoxide, methylene chloride, anddichloroethane.

In another aspect, the polar liquid is a ketone-containing liquid. Forexample, the ketone-containing liquid may have the formula R⁶—C(═O)—R⁶wherein R⁶ at each occurrence is independently selected from organicmoieties having 1-12 carbons, where two R⁶ moieties in a liquid may bejoined together to provide a cyclic ketone. For further example, theketone-containing polar liquid may be selected from acetone, methylethyl ketone, methyl isobutyl ketone and cyclohexanone.

In another aspect, the polar liquid is a sulfoxide-containing liquid.For example, the sulfoxide-containing liquid may have the formulaR⁸—S(═O)—R⁸ and R⁸ is independently selected at each occurrence fromC₁-C₆ alkyl.

In another aspect, the polar liquid is a glycol ether. For example, thepolar liquid may be a glycol ether of the formula R⁹—[O—R¹⁰—]_(n)—OHwherein R⁹ is a C₁-C₂₂ hydrocarbon, R¹⁰ is a C₂-C₆ hydrocarbonindependently selected at each occurrence, and n is an integer selectedfrom 1, 2, 3, 4, 5 and 6. As another example, the glycol ether may beethylene glycol mono phenyl ether, dipropyleneglycol mono methyl etheror tripropyleneglycol mono methyl ether.

In another aspect, the polar liquid may include, or may exclusively be,a liquid fragrance. Liquid fragrances are well known in the art and aresold by many companies.

In another aspect, the polar liquid may include, or may exclusively be,a liquid surfactant. Liquid surfactants are well known in the art andare sold by many companies.

In another aspect, the polar liquid may include, or may exclusively be,a liquid polyepoxy resin. Liquid polyepoxy resins are well known in theart and are sold by many companies.

In another aspect, the present invention provides ahydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymer ofthe formula

wherein, independently at each occurrence, R¹ is a C₁₋₈ hydrocarbonradical; R² is a C₂₋₄ hydrocarbon diradical; R³ is a C₂₋₅₂ hydrocarbondiradical, where at least 50% of the R³ diradicals are derived fromdimer acid; R⁴ is selected from C₂₋₈ hydrocarbon diradicals andpolyether diradicals of the formula —(R¹¹—O)_(g)—R¹¹— wherein R¹¹ is aC₂-C₆ hydrocarbon diradical independently selected at each occurrenceand g is an integer from 2 to 100; Z is selected from O and NH; x is aninteger from 2 to 100; y is an integer equal to 1 or more that providesa copolymer molecular weight of 2,000 to 50,000, and z is an integerfrom 2 to 100. This block copolymer may be combined with a polar liquidas described herein.

In another aspect, the present invention provides ahydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymerprepared by a process comprising reacting together reactants comprisingdimer acid, polyetherdiamine, alkylenediamine, and a monofunctionalpolyether having both hydrocarbon termination and termination selectedfrom amine, hydroxyl and carboxyl, under reaction conditions that formthe block copolymer. In further aspects, the present invention providesthat the polyetherdiamine and the monofunctional polyether in totalcontribute 20-45 wt % of the total weight of the reactants; thepolyetherdiamine has the formula H₂N—(R¹¹—O)_(g)—R¹¹—NH₂ wherein R¹¹ isa C₂-C₆ hydrocarbon diradical independently selected at each occurrence,g is an integer from 2 to 50, and the polyetherdiamine contributes 10-30wt % of the total weight of the reactants; the monofunctional polyetherhas the formula R¹—O—(R¹¹—O)_(h)—R¹¹—NH₂ wherein R¹ is a C₁₋₆hydrocarbon radical, R¹¹ is a C₂-C₆ hydrocarbon diradical independentlyselected at each occurrence, h is an integer from 2 to 50, and themonofunctional polyether contributes 5-20 wt % of the total weight ofthe reactants; the polyetherdiamine has the formulaH₂N—(R¹¹—O)_(g)—R¹¹—NH₂ wherein R¹¹ is a C₂-C₄ hydrocarbon diradicalindependently selected at each occurrence from ethylene, propylene andbutylene, g is an integer from 2 to 50, and the polyetherdiaminecontributes 10-30 wt % of the total weight of the reactants, and themonofunctional polyether has the formula R¹—O—(R¹¹—O)_(h)—R¹¹—NH₂wherein R¹ is a C₁₋₆ hydrocarbon radical, R¹¹ is a C₂-C₄ hydrocarbondiradical independently selected at each occurrence from ethylene,propylene and butylene, h is an integer from 2 to 50, and themonofunctional polyether contributes 5-20 wt % of the total weight ofthe reactants, and the alkylenediamine has the formula H₂N—R¹¹—NH₂wherein R¹¹ is a C₂-C₆ hydrocarbon diradical; and wherein dimer acid,polyetherdiamine, alkylenediamine, and monofunctional polyether in totalconstitute at least 75 wt % of the total weight of the reactants. Thisblock copolymer may be combined with a polar liquid according to thepresent invention, to provide gelled structures.

In another aspect, the present invention provides composition comprisingpolar liquid and block copolymer where the composition is either in agel form or is at elevated temperature, i.e., a temperature greater thanroom temperature (typically ca. 21° C.) and is in a liquid but uponcooling to room temperature the liquid composition will adopt a gelform.

These and related aspects of the present invention are described morefully herein.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the present invention provides a hydrocarbon-terminatedblock copolymer of the formula (1)hydrocarbon-polyether-polyamide-polyether-hydrocarbon  (1)

In formula (1), a hydrocarbon group contains only carbon and hydrogenatoms. A polyether groups contains 2 or more ether groups, i.e., groupsof the formula hydrocarbon-O-hydrocarbon, where the hydrocarbon of oneether group can also serve as the hydrocarbon of another ether group. Apolyamide group contains 2 or more amide groups, i.e., groups of theformula hydrocarbon-C(═O)—NR-hydrocarbon, where the hydrocarbon of oneamide group may, or may not, also serve as the hydrocarbon of anotheramide group, and R is hydrogen or a hydrocarbon. Essentially, R in theamide group is determined by the choice of diamine used in thepreparation of the polyamide block of the block copolymer of the presentinvention. In one aspect, at least one amide group of the polyamide isflanked by polyether groups, while in another aspect all of the amidegroups in the polyamide block are flanked by hydrocarbon groups.

Suitable hydrocarbon groups are formed from one or more of aliphatic andaromatic moieties. Suitable aliphatic moieties are alkyl, alkylene,alkenyl, alkenylene, alkynyl, alkylnylene, cycloalkyl, cycloalkylene,cycloalkenyl, cycloalkenylene, cycloalkynyl, and cycloalkynylenemoieties. Aromatic moieties are also referred to herein as aryl groups.The hydrocarbon groups that terminate the block copolymers of thepresent invention will be referred to herein as R¹.

As used herein, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, andcycloalkynyl are monovalent radicals, while alkylene, alkenylene,alkynylene, cycloalkylene, cycloalkenylene, and cycloalkynylene arepolyvalent radicals. As used herein alkyl, alkylene, cycloalkyl, andcycloalkylene are saturated radicals, while alkenyl, alkenylene,alkynyl, alkylnylene, cycloalkenyl, cycloalkenylene, cycloalkynyl, andcycloalkynylene are unsaturated radicals. The alkyl, alkylene, alkenyl,alkenylene, alkynyl, and alkynylene moieties may be straight chain orbranched. The cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkylene,cycloalkenylene and cycloalkynylene moieties may be monocyclic orpolycyclic, where a polycyclic moiety may be, for example, bicyclic ortricyclic.

Exemplary alkyl moieties are methyl, ethyl, propyl, hexyl, and2-ethylhexyl. Exemplary alkylene moieties are methylene (—CH₂—),methylidene (═CH₂), and ethylene (—CH₂CH₂—). Exemplary cycloalkyl groupsare cyclohexyl and norbornyl.

Suitable aromatic moieties are monocyclic or polycyclic. An exemplarymonocyclic aryl group is phenyl, while exemplary polycyclic aryl groupsare naphthyl and fulverenyl. The aromatic moiety may be monovalent,e.g., phenyl, or polyvalent, e.g., phenylene.

The hydrocarbon group may be a combination of aromatic and aliphaticgroups. For example, benzyl (phenyl-CH₂—, an arylalkylene group), tolyl(CH₃-phenylene-, an alkylarylene group), and xylyl ((CH₃)₂-phenylene-, adialkylarylene group). The hydrocarbon group may be a combination of twoor more aromatic groups, e.g., biphenyl (phenyl-phenylene-, anarylarylene group).

The R¹ group necessarily contains at least one carbon. In oneembodiment, the R¹ group contains 1-32 carbons. In one embodiment, theR¹ alkyl group contains 1-12 carbons. In one embodiment, R¹ is an alkylgroup containing 1-4 carbons. In one embodiment, the R¹ group is analkyl group. In one embodiment, the R¹ alkyl group is straight-chained.In one embodiment, the R¹ alkyl group is branched. In one embodiment, R¹is methyl.

The block copolymer of formula (1) contains at least two polyetherblocks. As its name implies, a polyether block contains a plurality ofether groups, i.e., groups of the formula —C—O—C—. In other words, apolyether block contains the repeating formula —O—R²— where R² is ahydrocarbon group. In one aspect, R² is an alkylene group. The alkylenegroup R² may be aliphatic (saturated and/or unsaturated) or aromatic,straight chain and/or branched, independently at each occurrence in thepolyether block. In one aspect, R² has 1-6 carbons at each occurrence inthe polyether block, while in another aspect R² has 2-4 carbons at eachoccurrence. In one aspect, R² has the formula —CH₂—CH(R^(2a))— whereinR^(2a) is selected from hydrogen, methyl and ethyl.

In one aspect, the polyether component of the block copolymer has amolecular weight (measured as either number or weight average) of lessthan 10,000. In another aspect, the molecular weight is between 100 and4,000.

The block copolymer of formula (1) contains a polyamide block. As itsname implies, the polyamide block contains a plurality of amide groups,i.e., groups of the formula —NH—C(═O)— and/or —C(═O)—NH—. In thepolyamide block, two or more amide groups are separated by hydrocarbongroups, e.g., alkylene groups and/or polyether groups.

In one aspect, the polyamide block contains —C(═O)—R³—C(═O)— moietieswherein R³ is a hydrocarbon group. In one aspect, the polyamide blockincludes R³ groups having at least 30 carbons. In one aspect, thepolyamide block includes R³ groups having 30-42 carbons.

In one aspect, the polyamide block includes R³ groups that are formedfrom fatty acid polymerization. Fatty acids derived from vegetable oils,tallow, and tall oil (the latter are known as tall oil fatty acids, orTOFA) are commonly subjected to thermal polymerization, typically in thepresence of a clay catalyst, to provide a commercially-available productknown as dimer acid. These fatty acids contain 18 carbons, so thatcorresponding dimer acid consists mainly of C₃₆ dicarboxylic acids. Thisdimer acid may be denoted by the structure HOOC—C₃₄—COOH, where the C₃₄group is an exemplary R³ group of the present invention. C₃₄ is amixture of isomeric structures, as more fully described in detaileddescriptions of dimer acid, as found in, for example, NavalStores—Production, Chemistry and Utilization, D. F. Zinkel and J. Russel(eds.), Pulp. Chem. Assoc. Inc., 1989, Chapter 23.

Suitable polymerized fatty acids are available commercially as, forexample, UNIDYME™ dimer acid, from Arizona Chemical, company ofInternational Paper, (Jacksonville, Fla.), EMPOL™ dimer acid from HenkelCorporation (now Cognis @cognis.com, Cincinnati, Ohio); and PRIPOL™dimer acid from Unichema North America (Chicago, Ill.).

Dimer acid, as commercially available, typically contains someby-products of the fatty acid polymerization process. One commonbyproduct is so-called trimer acid, which results when three fatty acidmolecules react together to form a C₆₄ tricarboxylic acid. It mayhappen, in the preparation of a block copolymer of the presentinvention, that two of the carboxylic acid groups of trimer acid willreact with, e.g., a diamine, leaving one carboxylic acid groupunreacted. When this occurs, the block copolymer will contain acarboxylic acid-substituted R³ group, which is technically not ahydrocarbon. Accordingly, while block copolymers of the presentinvention contain hydrocarbon groups between two NHC(═O) groups, theymay also contain some, typically a minor amount, of carboxylicacid-substituted hydrocarbon groups between two NHC(═O) groups. Forconvenience, as used herein, C₃₄ refers to the incorporation of dimeracid into a polyamide block, where C₃₄ includes the reaction product ofsome trimer acid that may be a by-product in the commercial dimer acid.

In one aspect, the present invention provides block copolymers offormula (1) wherein each of the C(═O) groups is bonded to C₃₄, i.e., theblock copolymer is formed from dimer acid as the exclusive polyacidreactant. However, in another aspect, the polyamide block includes bothC₃₄ and “co-diacid”-derived R³ groups. Thus, the polyamide block may beformed by reacting both dimer acid and co-diacid with a diamine.However, in a preferred embodiment of the invention, dimer acid is usedwithout any co-diacid in preparing the polyamide block of the blockcopolymer.

As used herein, a co-diacid is a compound of formula HOOC—R³—COOH whereR³ is not C₃₄ as defined above. In one aspect, the polyamide block incopolymers of formula (1) includes R³ groups having 2-32 carbons, whichare referred to herein a co-diacid R³ groups. Suitable co-diacids have alinear C₄₋₁₂ hydrocarbon group between the two carboxylic acid groups,and more preferably have a linear C₆₋₈ hydrocarbon group. Linear diacidssuitable for the present invention include 1,6-hexanedioic acid (adipicacid), 1,7-heptanedioic acid (pimelic acid), 1,8-octanedioic acid(suberic acid), 1,9-nonanedioic acid (azelaic acid), 1,10-decanedioicacid (sebacic acid), 1,11-undecanedoic acid, 1,12-dodecanedioic acid(1,10-decanedicarboxylic acid), 1,13-tridecanedioic acid (brassylicacid) and 1,14-tetradecanedioic acid (1,12-dodecanedicarboxylic acid).

Another exemplary co-diacid for use in the present invention is thereaction product of acrylic or methacrylic acid (or the ester thereof,with a subsequent hydrolysis step to form an acid) and an unsaturatedfatty acid. For example, a C₂₁ diacid of this type may be formed byreacting acrylic acid with a C₁₈ unsaturated fatty acid (e.g., oleicacid), where an ene-reaction presumably occurs between the reactants. Anexemplary C₂₁ diacid is commercially available from WestvacoCorporation, Chemical Division, Charleston Heights, S.C., as theirproduct number 1550.

Aromatic diacids may be used as the co-diacid. An “aromatic diacid” asused herein is a molecule having two carboxylic acid groups (—COOH) orreactive equivalents thereof (e.g., acid chloride (—COCl) or ester(—COOR)) and at least one aromatic ring (“Ar”). Phthalic acids, e.g.,isophthalic acid and terephthalic acid, are exemplary aromatic diacids.The aromatic diacid may contain aliphatic carbons bonded to the aromaticring(s), as in HOOC—CH₂—Ar—CH₂—COOH and the like. The aromatic diacidmay contain two aromatic rings, which may be joined together through oneor more carbon bonds, (e.g., biphenyl with carboxylic acid substitution)or which may be fused (e.g., naphthalene with carboxylic acidsubstitution).

In one aspect, the C₃₄ R³ groups constitute at least 50 mol % of thetotal of the R³ groups. In other aspects, the C₃₄ R³ groups constituteat least 60 mol %, or 70 mol %, or 80 mol %, or 90 mol %, or 95 mol % ofthe R³ groups. Stated another way, dimer acid contributes at least 50%of the diacid equivalents, or at least 60-%, or 70%, or 80%, or 90%, or95% of the diacid equivalents in the polyamide block of the copolymer offormula (1). In one aspect of the invention, only dimer acid is used toform the block copolymer, i.e., no co-diacid is among the reactants.

As mentioned above, in one aspect of the present invention, thepolyamide block contains —C(═O)—R³—C(═O)— moieties wherein R³ is ahydrocarbon group. As discussed above, in a preferred aspect thepolyamide block includes R³ groups having at least 30 carbons, morepreferably the polyamide block includes R³ groups having 30-42 carbons,and still more preferably includes R³ groups that have the structure ofdimer acid with the exception that the carboxylate groups are missing.While in a preferred aspect of the invention the polyamide block isprepared from dimer acid, optionally with co-diacid, in anotherpreferred aspect of the invention the polyamide block is preparedwithout dimer acid, i.e., is prepared with only co-diacid.

In one aspect of the invention, the polyamide block contains thecyclohexane diradical between at least two carbonyl groups. The carbonylgroups are preferably located at opposite carbons of the cyclohexanegroup, i.e., the R³ cyclohexane group has the following structure (2)

In one aspect, all of the R³ groups in the block copolymer contain thecyclohexyl group (2). In another aspect, at least 50% of the R³ groupsin the block copolymer contain the cyclohexyl group (2). In anotheraspect, at least 25% of the R³ groups in the block copolymer contain thecyclohexyl group (2). The introduction of an R³ group of structure (2)into a diblock copolymer of the present invention is readilyaccomplished by including cyclohexanedicarboxylic acid (CHDA) among thecopolymer-forming reactants. CHDA, including 1,4-CHDA, is commerciallyavailable from many sources, e.g., Aldrich (Milwaukee, Wis.;@sigma-aldrich.com).

In one aspect, the polyamide block contains —NH—R⁴—NH— moieties whereinR⁴ is a hydrocarbon group. In one aspect, the R⁴ hydrocarbon group has1-20 carbons. In one aspect, the polyamide block includes R⁴ groupshaving 1-10 carbons. In one aspect, the R⁴ group is an alkylene group.In one aspect, R⁴ is a straight-chained alkylene group. In one aspect,the polyamide block includes R⁴ groups having 2 carbons, while inanother aspect at least 50% of the R⁴ groups have 2 carbons, while inanother aspect all of the R⁴ groups have 2 carbons.

When the R³ group of the polyamide block is most often the cyclohexanediradical, i.e., when at least 50% of the R³ groups are cyclohexanediradical, then the R⁴ group preferably has at least 6 carbons. This isbecause when R⁴ has only 2-4 carbons, the melting point of the resintends to increase. Likewise, as more of the R³ groups are cyclohexanediradical, the melting point of the resin tends to increase.Accordingly, when at least about 50% of the R³ groups are cyclohexanediradical, then most if not all of the R⁴ groups should have at least 6carbons in order to counteract the melting point-increasing effect ofthe cyclohexane diradical.

The melting point of the resin should not be too high or else it will bedifficult to dissolve the resin in a polar liquid. Typically, the resinand polar liquid are heated until the resin melts, and then thecomposition is stirred to provide a homogeneous solution at elevatedtemperature. Upon cooling, this homogenous solution typically forms agel. When the melting point of the resin exceeds the boiling point ofthe polar liquid, then the resin cannot be heated to its melting pointin the solvent, and dissolution of the resin in the solvent becomes moredifficult and time-consuming. Thus, it is preferred that the resin havea melting point of less than about 250° C., more preferably less thanabout 200° C. In another aspect, it is preferred that the resin have amelting point that is less than, or within about 25° C. of, the boilingpoint of the polar liquid. When all of the R³ groups in the resin arecyclohexane diradical, and all of the R⁴ groups have only two carbons,the resulting resin has a melting point in excess of about 300° C., andsuch a high melting resin is very difficult to dissolve in a polarliquid. Certainly, even when all of the R³ groups are cyclohexanediradical, a very small amount of the R³ groups may have only 2 carbons,and still provide a resin that can be dissolved in many solvents atelevated temperature.

In one aspect, the polyamide block contains —NH—R⁴—NH— moieties whereinR⁴ is a polyether group. As defined above, a polyether block contains aplurality of ether groups, i.e., groups of the formula —C—O—C—. In otherwords, a polyether block contains the repeating formula —O—R²— where R²is a hydrocarbon group. In one aspect, R² is an alkylene group. Thealkylene group R² may be aliphatic (saturated and/or unsaturated) oraromatic, straight chain and/or branched, independently at eachoccurrence in the polyether block. In one aspect, R² has 1-6 carbons ateach occurrence in the polyether block, while in another aspect R² has2-4 carbons at each occurrence. In one aspect, R² has the formula—CH₂—CH(R^(2a))— wherein R^(2a) is selected from hydrogen, methyl andethyl.

In one aspect, the polyether component of the R⁴ potion of the blockcopolymer of the present invention has a molecular weight (number orweight average) of less than 10,000. In another aspect, the molecularweight is between 100 and 4,000.

Compounds of the formula H₂N—R⁴—NH₂ are commonly known as diamines, andare available from a large number of vendors. Compounds of the formulaHOOC—R³—COOH are commonly known as diacids, or dibasic acids, and arelikewise available from a large number of vendors. Aldrich (Milwaukee,Wis.; @sigma-aldrich.com); EM Industries, Inc. (Hawthorne, N.Y.;@emscience.com); Lancaster Synthesis, Inc. (Windham, N.H.;@lancaster.co.uk) are three representative vendors.

In formula (1), the bond ‘—’ between hydrocarbon and polyetherrepresents a C—O bond where the carbon is contributed by the hydrocarbonand the oxygen is contributed by the polyether.

In formula (1), in one aspect, the bond between polyether and polyamideis C—NH—C(═O)—C where C—NH may be seen as being contributed by thepolyether and C(═O)—C may be seen as being contributed by the terminalacid group of a polyamide. Block copolymers according to this aspect maybe formed by, for example, reacting an amino and hydrocarbon terminatedpolyether of the formula R¹—(O—R²—)NH₂ with a carboxylic acid terminatedpolyamide of the formula HOOC—NH—R⁴—NH-etc. so as to formR¹—(O—R²—)N—C(═O)—R⁴. Thus, an amide group may be present as the linkbetween polyether and polyamide in formula (1).

In formula (1), in one aspect, the bond between polyether and polyamideis C—C(═O)—NH—C where C—C(═O) may be seen as being contributed by thepolyether and NH—C may be seen as being contributed by the terminalamine group of a polyamide. Block copolymers according to this aspectmay be formed by, for example, reacting a carboxylic acid andhydrocarbon terminated polyether of the formula R¹—(O—R²—)COOH with anamine terminated polyamide of the formula H₂N—R⁴—NH—C(═O)—R³-etc. so asto form R¹—(O—R²—)—C(═O)—NH—R⁴—NH—C(═O)—R³-etc. Thus, once again, anamide group may be present as the link between polyether and polyamidein formula (1). However, urethane groups are preferably not a part ofthe block copolymer of the present invention.

In formula (1), in one aspect, the bond between polyether and polyamideis C—O—C(═O)—C where C—O may be seen as being contributed by thepolyether and C(═O) may be seen as being contributed by the terminalacid group of a polyamide. Block copolymers according to this aspect maybe formed by, for example, reacting a hydroxyl and hydrocarbonterminated polyether of the formula R¹—(O—R²—)OH with a carboxylic acidterminated polyamide of the formula HOOC—NH—R⁴—NH-etc. so as to formR¹—(O—R²—)O—C(═O)—R⁴. Thus, an ester group may be present as the linkbetween polyether and polyamide in formula (1). In various aspects ofthe invention, the block copolymer contains 0 ester groups (e.g., whenthe polyether is amine terminated rather than hydroxyl terminated), orno more than 1 ester group (when a mixture of amine terminated andhydroxyl terminated polyether are used), or no more than 2 ester groups.

In one aspect, the present invention provides a composition comprising ahydrocarbon-terminated polyether-polyamide block copolymer of thepresent invention having an acid number of less than 25, or less than20, or less than 15, or less than 10. The hydrocarbon-terminatedpolyether-polyamide block copolymer of formula (1) does not have anyfree carboxylic acid groups, and accordingly has an acid number of zero.However, when prepared from diacid, diamine and hydrocarbon-terminatedpolyether according to a process described herein, some of the diacidmay not react with the diamine and/or polyether, and according the finalproduct may have some unreacted carboxylic acid that will be responsiblefor the product having an acid number greater than zero. Preferably, theproduct has a minor amount of this unreacted diacid, and thus has only asmall acid number. Esterification catalysts may be used to encourage allof the diacid to react with hydroxyl groups, so as to minimize theamount of free acid, i.e., to reduce the acid number of the product.

In one aspect, the present invention provides a composition comprising ahydrocarbon-terminated polyether-polyamide block copolymer of thepresent invention having an amine number of less than 25, or less than20, or less than 15, or less than 10, or less than 5 or less than 2 orless than 1. The hydrocarbon-terminated polyether-polyamide blockcopolymer of formula (1) does not have any free amine groups, andaccordingly has an amine number of zero. However, when prepared fromdiacid, diamine and hydrocarbon-terminated polyether according to aprocess described herein, some of the diamine may not react with thediacid, and according the final product may have some unreacted aminegroups that will be responsible for the product having an amine numbergreater than zero. Preferably, the product has a minor amount of thisunreacted diamine, and thus has only a small amine number. Amidificationcatalysts may be used to encourage all of the diamine to react withcarboxyl groups, so as to minimize the amount of free amine, i.e., toreduce the amine number of the product.

In one aspect, the present invention provides hydrocarbon-terminatedpolyether-polyamide block copolymers, and compositions containing thesecopolymers, that has a softening point of 50-150° C. (Ring and Ball, orMettler). In another aspect, the softening point is 75-125° C., while inanother aspect the softening point is 75-100° C., while in anotheraspect the softening point is 80-120° C.

In one aspect, the present invention provides hydrocarbon-terminatedpolyether-polyamide block copolymers, and compositions containing thesecopolymers, that has a weight or number average molecular weight of2,000 to 30,000. The molecular weight is measured by preparing asolution of the copolymer or composition in a suitable solvent, e.g.,tetrahydrofuran (THF) and identifying the retention time of thecopolymer by gel permeation chromatography, and comparing that retentiontime to the retention times of solutions of polystyrene having knownmolecular weight characterizations. In one aspect, the copolymers have aweight or number average molecular weight of greater than 1,000. Inanother aspect, the copolymers have a weight average molecular weight ofup to 50,000. In other aspects, the copolymers have a weight averagemolecular weight in the range of 2,000 to 50,000; 5,000 to 50,000; 5,000to 25,000; and 10,000 to 25,000. The molecular weight can be controlledby controlling the ratio of monofunctional to difunctional reactants.Among other features, the hydrocarbon termination on the polyetherreactant allows for control of the molecular weight of the copolymer. Ifboth ends of the polyether reactant were reactive, e.g., the polyethercontained hydroxyl functionality at both ends, then the polyether couldnot be utilized as a terminator in the preparation of copolymers of thepresent invention.

In one aspect, the present invention provides hydrocarbon-terminatedpolyether-polyamide block copolymers, and compositions containing thesecopolymers, that have a viscosity, as measured on the neat copolymer orcomposition at 160° C., of less than 5,000 centipoise (cPs, or cps), orless than 4,000 cPs, or less than 3,000 cPs, or less than 2,000 cPs, orless than 1,000 cPs Typically, the copolymer and compositions will havea melt viscosity, as measured on the neat copolymer or composition at160° C., of more than 50 cPs, typically more than 500 cPs.

In one aspect, the present invention provides ahydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymer ofthe formula

wherein, independently at each occurrence, R¹ is a C₁₋₈ hydrocarbonradical; R² is a C₂₋₄ hydrocarbon diradical; R³ is a C₂₋₅₂ hydrocarbondiradical, where at least 50% of the R³ diradicals are derived fromdimer acid; R⁴ is selected from C₂₋₈ hydrocarbon diradicals andpolyether diradicals of the formula —(R¹¹—O)_(g)—R¹¹— wherein R¹¹ is aC₂-C₆ hydrocarbon diradical independently selected at each occurrenceand g is an integer from 2 to 100; Z is selected from O and NH; x is aninteger from 2 to 100; y is an integer equal to 1 or more that providesa copolymer molecular weight of 2,000 to 50,000, and z is an integerfrom 2 to 100. The value of y can be controlled simply by adjusting theratio of monofunctional to difunctional reactants.

Block copolymers of the present invention may be prepared by reactingtogether compounds of the formulae R¹—(O—R²)_(x)—W, HOOC—R³—COOH, andH₂N—R⁴—NH₂, where W represents either an amine, hydroxyl or carboxylicacid group. As used herein an amine group (—NH₂), a carboxylic acidgroup (—COOH) and a hydroxyl group (—OH) include reactive equivalentsthereof. For instance, HOOC—R³—COOH includes reactive equivalents, suchas monoesters and diesters, i.e., compounds wherein a carboxylic acid isin esterified form.

Compounds of the formula R¹—(O—R²)_(x)—W wherein W is hydroxyl are alsoknown as ether-terminated polyalkylene glycols. These compounds aregenerally well known and may be readily prepared by methodologydescribed in the scientific and patent literature. For example, amonohydric initiator, i.e., a compound of the formula R¹—OH is reactedwith an alkylene oxide (an R² group that includes an epoxide group),e.g., ethylene oxide, propylene oxide, etc. to provide a compound of theformula R¹—(O—R²)_(x)—OH. These compounds are available from, e.g.Aldrich Chemical (Milwaukee, Wis.).

In one aspect, block copolymers are prepared from compounds of formulaR¹—(O—R²)_(x)—W wherein W is hydroxyl and R² is ethylene (—CH₂CH₂—).Such compounds of formula R¹—(O—R²)_(x)—W may be referred to herein asethoxylates or alcohol ethoxylates. Ethoxylates may be obtained frommany commercial sources (e.g., Dow, Midland Mich.) or may be prepared byreacting alcohols of formula R¹—OH with ethylene oxide to give thestructure (2) belowR¹—O—(CH₂CH₂O)_(m)—H  (2)where R¹ is a hydrocarbon group as defined previously, and in one aspectR¹ is a C₆₋₂₂ alkyl or aralkyl group. Ethoxylates are typicallycolorless liquids to low melting point pasty solids depending on thechain length (m). Exemplary ethoxylates having various combinations ofR¹ groups and molecular weight are given in TABLE A (TABLE A—TYPICALETHOXYLATES AND THEIR PROPERTIES). In TABLE A, Manuf. is an abbreviationfor manufacturer, EO is an abbreviation for ethylene oxide, % EO refersto the weight percent ethylene oxide in the product, EO/OH refers to themolar ratio of ethylene oxide to hydroxyl, HLB refers to the hydrophilelipophile balance, Shell refers to the Shell Chemical division of theRoyal Dutch/Shell Group of Companies (@shell.com) where Shell sellsalcohol ethoxylates under the NEODOL™ trademark. Also in TABLE A, Condearefers to CONDEA Vista Company (Houston, Tex.; @condea.de) which sells anumber of alcohol ethoxylates under their brand names NONFIX™, BIODAC™,LORODAC™, LIALET™, EMULDAC™ and ALFONIC™ where these materials differ bythe R¹ group, and the number of ethylene oxide groups in the product.

TABLE A Typical Ethoxylates and Their Properties Ethoxylate Manuf. R¹ %EO EO/OH MW HLB NEODOL ™ Shell C₁₂₋₁₃ 60 6.6 484 12 23-6.5 NEODOL ™Shell C₁₄₋₁₅ 71.8 12.9 790 14.4 45-13 NEODOL ™ Shell C₉₋₁₁ 69.7 8.3 52413.9 91-8 ALFONIC ™ Condea C₆₋₁₀ 50 3.1 276 10 610-3.5 ALFONIC ™ CondeaC₁₆₋₁₈ 46 5.1 469 9 1618-5

In another aspect, block copolymers are prepared from compounds offormula R¹—(O—R²)_(x)—W wherein W is hydroxyl and R² is, independentlyat each occurrence, selected from ethylene (—CH₂CH₂—), propylene(—CH₂—CH(CH₃)—) and n-butylene (—CH₂—CH(CH₂CH₂)—). Such compounds offormula R¹—(O—R²)_(x)—W may be referred to herein as polyalkylene glycolderivatives. Polyalkylene glycol derivatives may be obtained from manycommercial sources (e.g., Dow, Midland Mich.; Union Carbide, Danbury,Conn.; Aldrich, Milwaukee, Wis.) or may be prepared by reacting alcoholsof formula R¹—OH with ethylene oxide and/or propylene oxide to give thestructure (3) below:R¹—[O(CH₂CH₂O)_(z)(CH₂CH(CH₃)O)_(y)]—H  (3)

As commercially available, R¹ of the polyalkylene glycol derivative iscommonly methyl or n-butyl, but R¹ can be any hydrocarbon group. Sometypical properties of these materials, which are available from, e.g.,Union Carbide and Dow, are given in TABLE B (TABLE B—TYPICAL GLYCOLDERIVATIVES AND THEIR PROPERTIES). In TABLE B, MPEG stands for methylether poly(ethylene glycol) (i.e., R¹ is methyl and the repeating unitis always ethylene so that Y=0), MBPPG stands for monobutyl etherpoly(propylene glycol) (i.e., R¹ is butyl and the repeating unit isalways propylene so that Z=0), and MBPEGCPG stands for monobutyl etherpoly(ethylene glycol-co-propylene glycol), 50/50 PPG/PPE (i.e., R¹ isbutyl and the repeating unit is both ethylene and propylene, so that Zand Y are each equal to or greater than 1).

TABLE B Typical Polyalkylene Glycol Derivatives and Their PropertiesT_(m) (° C.) or Visc Glycol Manuf. R¹ MW @ 20° C. (cSt) MPEG 350 DOW CH₃350 −8 MPEG 550 DOW CH₃ 550 20 MPEG 750 DOW CH₃ 750 30 MPEG 2000 AldrichCH₃ 2000 52 MBPPG 340 Aldrich CH₃(CH₂)₃ 340 20 MBPPG 1000 AldrichCH₃(CH₂)₃ 1000 140 MBPPG 2500 Aldrich CH₃(CH₂)₃ 2500 1,300 MBPEGCPG 1700Aldrich CH₃(CH₂)₃ 1700 350 MBPEGCPG 3900 Aldrich CH₃(CH₂)₃ 3900 3,600

In another aspect, block copolymers are prepared fromhydrocarbon-terminated polyethers of the formula R¹—(O—R²)_(x)—W whereinW is carboxylic acid. These reactants are also known as oxa acids. Thesecompounds are generally well known and may be readily prepared bymethodology described in the scientific and patent literature. Forexample, a monohydric initiator, i.e., a compound of the formula R¹—OH,is reacted with an alkylene oxide (an R² group derived from an epoxidegroup), e.g., ethylene oxide, propylene oxide, etc., to provide acompound of the formula R¹—(O—R²)_(x)—OH. This R¹-terminatedpolyalkylene glycol is then subjected to oxidation conditions to convertthe terminal hydroxyl group to a carboxylic acid group. The resultantoxa acids have the structure (4) shown below, when prepared fromethylene oxide:R¹—O—(CH₂CH₂O)_(m)—CH₂—COOH  (4).Compounds of formula (4) where m=1 or 2 are available from Hoechst (nowAventis), as experimental products. Some properties of these acids aregiven in TABLE C (TABLE C—TYPICAL OXA ACIDS AND THEIR PROPERTIES). InTABLE C, AN stands for acid number.

TABLE C Typical Oxa Acids and Their Properties Visc @ AN Acid m MW 20°C. (mP) (mg KOH/g) 3,6-dioxaheptanoic acid 1 134.1 35 4103,6,9-trioxadecanoic acid 2 178.2 73 310

In another aspect, block copolymers are prepared from compounds offormula R¹—(O—R²)_(x)—W wherein W is amine and R² is one or more ofethylene (—CH₂CH₂—), propylene (—CH₂—CH(CH₃)—), and n-butylene(—CH₂—CH(CH₂CH₂)—), each independently selected at each occurrence. Suchcompounds of formula R¹—(O—R²)_(x)—W may be referred to herein aspolyoxyalkyleneamines. These compounds are generally well-known to oneof ordinary skill in the art and may be readily prepared by methodologydescribed in the scientific and patent literature. For example, amonohydric initiator, i.e., a compound of the formula R¹—OH, is reactedwith an alkylene oxide (an R² group is derived from anepoxide-containing group), e.g., ethylene oxide, propylene oxide, etc.,to provide a compound of the formula R¹—(O—R²)_(x)—OH. ThisR¹-terminated polyalkylene glycol is the subjected to reactionconditions to convert the terminal hydroxyl group to a terminal aminogroup, e.g., ammonia and hydrogen.

As commercially available, polyoxyalkyleneamines (also known aspoly(oxyalkylene) monoamines) generally have the structure (5) below:R¹—OCH₂CH₂O—(CH₂CHR′O)_(x)—CH₂CH(R″)NH₂  (5)where R¹ is preferably an alkyl group; R′ is preferably H, CH₃, or C₂H₅;and R″ is preferably H or CH₃. Common commercially-availablepolyoxyalkyleneamines are typically prepared from ethylene oxide and/orpropylene oxide and are available commercially in varying ratios ofpropylene oxide-to ethylene oxide-based residues. Polyoxyalkyleneaminesmay be obtained from, e.g., BASF, Mt. Olive, N.J., and HuntsmanChemical, Salt Lake City, Utah. Commercially availablepolyoxyalkyleneamines and selected properties are given in TABLE D(TABLE D—TYPICAL POLYOXYALKYLENEAMINES AND THEIR PROPERTIES). In TABLED, both XTJ and JEFFAMINE® are product identifiers used by HuntsmanChemical. In TABLE D, R′ is H (when ethylene oxide (EO) is the reactant)or —CH₃ (when propylene oxide (PO) is the reactant), where TABLE Dprovides the PO/EO ratio in the designated polyoxyalkyleneamine.

TABLE D Typical Polyoxyalkyleneamines and Their Properties PO/EO T_(m)amine R¹ R″ (mole ratio) MW (° C.) XTJ-505 CH₃ CH₃ 9/1 600 −40 XTJ-506CH₃ CH₃  3/19 1,000 29 XTJ-507 CH₃ CH₃ 39/6  2,000 −36 XTJ-508(formerlyCH₃ CH₃ 10/32 2,000 17 JEFFAMINE ® M-2070 XTJ 234 CH₃ CH₃  8/49 3000 36Diglycol amine H H 0/2 105 (m = 0)

Thus, the present invention discloses the use of monofunctionalpolyethers having both hydrocarbon termination and termination selectedfrom amine, hydroxyl and carboxyl, in the preparation of resincompositions comprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon, where examples ofthe monofunctional polyether are disclosed above as ethoxylates,polyalkylene glycol derivatives, oxa acids, and polyoxyalkyleneamines.

In addition to the monofunctional polyether, the block copolymers of thepresent invention are prepared from diamines, where the diamine may be,for example, an alkylene diamine (i.e., a diamine of the formulaH₂N—R⁴—NH₂ where R⁴ is a hydrocarbon) or a polyetherdiamine (i.e., adiamine of the formula H₂N—R⁴—NH₂ wherein R⁴ is a polyether, wherepolyethers are organic moieties having a plurality of ether groups).

Thus, the diamine may be an alkylene diamine having R⁴ hydrocarbongroups as described herein. Exemplary alkylene diamines, most or all ofwhich are commercially available include, without limitation,ethylenediamine (EDA), 1,2-diaminopropane, 1,3-diaminopropane,1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,3-diaminopentane,1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,6-hexanediamine(also known as hexamethylenediamine, HMDA), 2-methyl-1,5-pentanediamine,1,7-diaminoheptane, 1,8-diaminooctane, 2,5-dimethyl-2,5-hexanediamine,1,9-diaminononane, 1,10-diaminodecane, 1,12-diaminododecane,diaminophenanthrene (all isomers, including 9,10),4,4′-methylenebis(cyclohexylamine), 2,7-diaminofluorene, phenylenediamine (1,2; 1,3 and/or 1,4 isomers), adamantane diamine,2,4,6-trimethyl-1,3-phenylenediamine, 1,3-cyclohexanebis(methylamine),1,8-diamino-p-menthane, 2,3,5,6-tetramethyl-1,4-phenylenediamine,diaminonaphthalene (all isomers, including 1,5; 1,8; and 2,3) and4-amino-2,2,6,6-tetramethylpiperidine. In one aspect, the diamine hasthe formula H₂N—R¹¹—NH₂ wherein R¹¹ is a C₂₋₆ hydrocarbon diradical.

The diamine may be a polyetherdiamine, also referred to herein as a PAO(for polyalkyleneoxy) diamine. Polyetherdiamines may be obtained fromTomah Products, Inc., Milton, Wis., and Huntsman Chemical. A suitablepolyetherdiamine is a poly(propyleneoxy)diamine having the formulaH₂N—C(CH₃)HCH₂O—(CH₂C(R)HO)_(n)—CH₂C(CH₃)H—NH₂, such as JEFFAMINE® 230diamine (n is 1-2, and R is CH₃), JEFFAMINE® D-400 diamine (n is 4-5 andR is CH₃), JEFFAMINE® D-2000 diamine (n is ca. 32 and R is CH₃), andXTJ-502 diamine (formerly JEFFAMINE® ED-2003 diamine, n is ca. 41 and Ris H), where each of these polyetherdiamines is commercially availablefrom Huntsman Corporation (Salt Lake City, Utah, USA, @huntsman.com).Another suitable diamine is a poly(ethyleneoxy)-co-propyleneoxy) diaminesuch as HUNTSMAN XTJ-500. Another suitable diamine is DPA-DEG, havingCAS Registry No. 271-79-0 and the chemical structureH₂N—CH₂CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂CH₂—NH₂. Yet another suitablediamine is XTJ-504 (formerly JEFFAMINE® EDR-148), which is also known astriethyleneglycoldiamine, having CAS Registry No. 929-59-9 and thechemical structure H₂N—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—NH₂. In one embodiment,the polyetherdiamine has the structureNH₂CH(CH₃)CH₂O—(CH₂CHR′O)_(x)—CH₂CH(CH₃)NH₂, where R and R′ are methylor H. Huntsman also sells triethyleneglycol diamine under their XTJ-504diamine designation (formerly JEFFAMINE® EDR-148 diamine) having thestructure H₂N—CH₂CH₂—O—CH₂CH₂—O—CH₂CH₂—NH₂, which may be used as thepolyetherdiamine. Additional suitable polyetherdiamines from Huntsmanare XTJ-511 having the structureH₂N—C(CH₃)CH₂—O—CH₂CH₂—O—CH₂CH₂—O—CH₂C(CH₃)H—NH₂; and XTJ-523 diaminehaving the structureH₂N—C(CH₂CH₃)H—CH₂—(O—C(CH₂CH₃)H—CH₂)_(a)—OCH₂C(CH₂CH₃)—NH₂ where a isca. 26.

In one aspect, the present invention provides ahydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymerprepared by a process comprising reacting together reactants comprisingdimer acid, polyetherdiamine, alkylenediamine, and a monofunctionalpolyether having both hydrocarbon termination and termination selectedfrom amine, hydroxyl and carboxyl, under reaction conditions that formthe block copolymer. Suitable reaction conditions are described herein.In a further aspect, the polyetherdiamine and the monofunctionalpolyether in total contribute 20-45 wt % of the total weight of thereactants. In a further aspect, the polyetherdiamine has the formulaH₂N—(R¹¹—O)_(g)—R¹¹—NH₂ wherein R¹¹ is a C₂-C₆ hydrocarbon diradicalindependently selected at each occurrence, g is an integer from 2 to 50,and the polyetherdiamine contributes 10-30 wt % of the total weight ofthe reactants. In a further aspect, the monofunctional polyether has theformula R¹—(R¹¹—O)_(h)—R¹¹—NH₂ wherein R¹¹ is a C₂-C₆ hydrocarbondiradical independently selected at each occurrence, h is an integerfrom 2 to 50, and the monofunctional polyether contributes 5-20 wt % ofthe total weight of the reactants. In a further aspect, thepolyetherdiamine has the formula H₂N—(R¹¹—O)_(g)—R¹¹—NH₂ wherein R¹¹ isa C₂-C₄ hydrocarbon diradical independently selected at each occurrencefrom ethylene, propylene and butylene, g is an integer from 2 to 50, andthe polyetherdiamine contributes 10-30 wt % of the total weight of thereactants; the monofunctional polyether has the formulaR¹—(R¹¹—O)_(h)—R¹¹—NH₂ wherein R¹¹ is a C₂-C₄ hydrocarbon diradicalindependently selected at each occurrence from ethylene, propylene andbutylene, h is an integer from 2 to 50, and the monofunctional polyethercontributes 5-20 wt % of the total weight of the reactants; and thealkylenediamine has the formula H₂N—R¹¹—NH₂ wherein R¹¹ is a C₂-C₆hydrocarbon diradical. In a further aspect, dimer acid,polyetherdiamine, alkylenediamine, and monofunctional polyether in totalconstitute at least 75 wt % of the total weight of the reactants.

Use of a significant level of both polyetherdiamine andpolyether-monoamine provides resins having the ability to form clearsolutions and/or clear gels in a wide range of polar liquids includingdimethylsulfoxide, propylene glycol, ethanol, polypropylene glycol andpolyethylene glycol and their monoalkyl ethers. At high weightpercentage use levels of terminator (i.e., hydrocarbon-terminatedpolyether), the resins are extremely soft. As the total level ofpolyether in the polyamide block decreases, the resin gains the feel andflexibility of a polyamide prepared from ethylene diamine and dimeracid, thus retaining some softness even at low levels of polyether. Someof these resins may dissolve in ethanol, and most demonstrated goodsolubility in propanol, however gelling behavior was infrequent. Ingeneral, propylene glycol is a preferred polar liquid from which toprepare gels containing polar liquid and resins of the invention (i.e.,resins prepared from polyetherdiamine and polyethermonoamine). Ingeneral, formation of dimer-acid based polyamides, even those includinga significant level of both polyether-diamine and polyethermonoamineamong the reactants leads to a resin that is not particularly compatiblewith glycerol.

In one aspect, the “significant level” of polyetherdiamine andpolyethermonoamine identified above is in the range of 20-45 wt %, wherethis range will, for convenience, be referred to herein as the“polyether” content of the resin. In other words, in every 100 grams ofresin-forming reactants, there are about 20-45 grams of polyether, wherethe remaining ca. 80-55 grams are contributed by diacid, preferablydimer acid and/or 1,4-cyclohexanedicarboxylic acid, and may includeoptional ingredients, where the resin is preferably made with someco-diamine, e.g., ethylene diamine. As a general rule, when thepolyether content of the resin is toward the lower part of this range,i.e., the resin has a polyether content of about 20-25 wt %, theresulting resin tends to be relatively better at gelling lower alcohols,e.g., ethanol and propanol. As another general rule, when the polyethercontent of the resin is toward the upper part of this range, i.e., theresin has a polyether content of about 40-45 wt %, the resulting resintends to be relatively better for gelling very polar liquids, e.g.,dimethylsulfoxide (DMSO) and propylene carbonate. When the polyethercontent is in the mid-range, i.e., the resin has a polyether content ofabout 25-40 wt %, or about 25-35 wt %, or about 30-35 wt %, theresulting resin tends to gel the largest number of polar solvents, i.e.,the resulting resin is a good gellant for most polar solvents.

The polyether content of the resin is due to the amount ofmono-functional polyether and di-functional polyether present in thereactants. As a general rule, increasing the relative amount ofmono-functional polyether within the starting materials used to preparethe resin will tend to decrease the average molecular weight of theresulting resin. In one aspect, the polyetherdiamine contributes 10-30wt % of the total weight of the reactants used to form the blockcopolymer. A preferred polyetherdiamine has the structureH₂N—(R¹¹—O)_(g)—R¹¹—NH₂ wherein R¹¹ is a C₂₋₆ hydrocarbon diradical(i.e., a diradical having 2, 3, 4, 5, or 6 carbons and hydrogens asneeded to fill all open valence sites of the carbons, but no otheratoms, also referred to as C₂-C₆ hydrocarbon diradical) independentlyselected at each occurrence, and g is an integer from 2 to 50. Apreferred polyetherdiamine has the structure of JEFFAMINE® D-400diamine. Additionally, or in an independent aspect, the monofunctionalpolyether may contribute 5-20 wt % of the total weight of the reactants.A preferred monofunctional polyether has the formulaR¹—O—(R¹¹—O)_(h)—R¹¹—NH₂ wherein R¹ is a C₁₋₆ hydrocarbon radical andR¹¹ is a C₂₋₆ hydrocarbon diradical independently selected at eachoccurrence, and h is an integer from 2 to 50. A preferred monofunctionalpolyether has the structure of JEFFAMINE® M-2070 monoamine.

When a polyetherdiamine and polyethermonoamine-derived resin isdissolved in a polar liquid, and then this solution is diluted withwater, it is typically observed that the solution remains homogeneous,i.e., the resin does not precipitate. Frequently, upon dilution withwater, the resin/polar liquid/water mixture takes on a bluish cast,indicating the presence of a microemulsion form.

In preparing the resins of the present invention, the diamine may be amixture of hydrocarbon diamine and polyetherdiamine. In addition, it isgenerally observed that increasing the level of termination, i.e.,increasing the relative amount of monoreactive hydrocarbon-terminatedpolyether, tends to provide a resin with a relatively lower softeningpoint and melt viscosity. The use of hexamethylene diamine (HMDA), inlieu of some or all of ethylene diamine (EDA), tends to lower thesoftening point of the resin. In one aspect of the invention, ethylenediamine is a reactant used in preparing the block copolymer, and inparticular is used in preparing the polyamide block of the blockcopolymer. Typically, EDA is blended with a polyetherdiamine, in orderto prepare the polyamide block of the block copolymer of the presentinvention, where the diamine(s) are reacted with diacid, e.g., dimeracid.

The inclusion of co-diacid, i.e., diacid other than dimer acid, e.g.,sebacic acid, in the reaction mixture tends to raise the softening pointof the resulting resin. The polyethermonoamine should not contain anyhydroxyl groups. The inclusion of hydroxyl groups is detrimental to thegelling ability of the resin made from the monoamine. Accordingly,hydroxyl terminated polyethers are not included within thepolyethermonoamine reactants of the present invention. Indeed, in oneaspect of the invention, no hydroxyl-containing materials, e.g.,alcohols (compounds containing one hydroxyl group) or polyols (compoundscontaining two or more hydroxyl groups), are used as a reactant toprepare a resin of the present invention. In one aspect, no polyol isincluded among the reactants to prepare a block copolymer of theinvention. In other aspects, if hydroxyl-containing materials areincluded as a reactant(s), then the hydroxyl-containing materialscontribute less than 5 wt %, or less than 3 wt %, of the total weight ofthe reactants.

Some of the inventive resins, particularly those prepared frompolyetherdiamines and polyether hydrocarbon-terminated monoamines, havethe unusual ability to form microemulsions in mixtures of water and apolar liquid. These blends are clear and homogeneous but have a distinctblue cast and can be either immobile gels or fluid liquids, depending onthe concentration of the resin and the polar liquid. They can be dilutedwith water without formation of a precipitate. Block copolymers of thepresent invention that form such microemulsions may be particularlyuseful as corrosion inhibitors in aqueous systems.

As described herein, diamines, dicarboxylic acids, andhydrocarbon-terminated polyethers having a reactive group W selectedfrom hydroxyl, amine and carboxyl are preferred starting materials toform the triblock copolymers of the invention. These starting materialsare preferably reacted together with a stoichiometry, and under reactionconditions, such that the acid number of the resulting block copolymeris less than 25, preferably less than 15, and more preferably less than10, while the amine number is preferably less than 10, more preferablyless than 5, and still more preferably less than 1. The softening pointof the block copolymer is preferably greater than room temperature, morepreferably is about 50° C. to about 150° C., and still more preferablyis about 75° C. to about 125° C.

It is important to control the stoichiometry of the reactants in orderto prepare a block copolymer according to the invention. The followingdiscussion regarding reactant stoichiometry uses the terms“equivalent(s)” and “equivalent percent”, where these terms are intendedto have their standard meanings as employed in the art. However, foradditional clarity, it is noted that equivalents refer to the number ofreactive groups present in a molar quantity of a molecule, such that amole of a dicarboxylic acid (e.g., sebacic acid) has two equivalents ofcarboxylic acid, while a mole of monoamine has one equivalent of amine.Furthermore, it is emphasized that in preparing a triblock copolymer ofthe invention, the diacid has only two reactive groups (both carboxylicacids, although dimer acid may contain a small amount of tricarboxylicacid), the diamine has only two reactive groups (both primary amines)and the hydrocarbon terminated polyether reactant has a single reactivegroup selected from amine, hydroxyl and carboxyl. Furthermore, these arepreferably, although not necessarily, the only reactive materialspresent in the reaction mixture.

When co-diacid is employed to prepare a block copolymer, the co-diacidpreferably contributes no more than about 50% of the equivalents ofcarboxylic acid present in the reaction mixture. Stated another way, theco-diacid contributes from 0-50 equivalent percent of the acidequivalents in the reaction mixture. Preferably, the co-diacidcontributes 0-30 equivalent percent, and more preferably contributes0-10 equivalent percent of the acid equivalents in the reaction mixture.

The stoichiometry of the reactants will have a significant impact on thecomposition of the block copolymer. For example, triblock copolymersmade with increasing amounts of polyether will tend to have lower(number and weight) average molecular weights. On the other hand, asless polyether is used, the average molecular weight of the moleculesthat comprise the block copolymer will increase. In general, increasingthe average molecular weight of the copolymer will tend to increase themelting point and melt viscosity of the copolymer. When a high meltingpoint copolymer is combined with a polar liquid to thereby form a gel,the gel will tend to have a firmer consistency than does a gel formedfrom a copolymer with a low melting point.

In order to prepare a block copolymer of the present invention, theabove-described reactants (diacid, diamine and polyether, or reactiveequivalents thereof) may be combined in any order. In one embodiment ofthe invention, the reactants are simply mixed together and heated for atime and at a temperature sufficient to achieve essentially completereaction, to thereby form the block copolymer. In another embodiment,the diacid and diamine are reacted together, followed by addition of themonoreactive polyether. During formation of the block copolymer, thediacid and diamine compounds will alternate to form what may be termedan alternating copolymer, i.e., the polyamide block of the blockcopolymer is an alternating copolymer of diacid and diamine. The terms“complete reaction” and “reaction equilibrium” as used herein haveessentially the same meaning, which is that further heating of theproduct does not result in any appreciable change in the acid or aminenumbers of the copolymer.

Thus, the block copolymer may be formed in a one-step procedure, whereinall of the diacid (including co-diacid), diamine (preferably includingethylene diamine) and polyether are combined and then heated to about180-250° C. for a few hours, typically 2-8 hours. When lowertemperatures are used, a longer reaction time is typically needed toachieve complete reaction. When the reaction temperature is too high,the reactants and/or products may undergo undesirable thermally-induceddecomposition. Typically, the reactants must be exposed to a temperaturein excess of 100° C. in order to drive off the water formed by thecondensation of the reactants. Since one or more of the reactants may bea solid at room temperature, it may be convenient to combine each of theingredients at a slightly elevated temperature, and then form ahomogeneous mixture prior to heating the reaction mixture to atemperature sufficient to cause reaction between the diacid, diamine andpolyether. Alternatively, although less preferably, two of the reactantsmay be combined and reacted together, and then the third reactant isadded followed by further heating until the desired product is obtained.Reaction progress may be conveniently monitored by periodicallymeasuring the acid and/or amine number of the product mixture.

As one example, dimer acid may be reacted with diamine so as to formpolyamide, and then this intermediate polyamide may be reacted withpolyether to form a hydrocarbon terminated polyether-polyamide-polyetherblock copolymer. Because the components of the block copolymer arepreferably in reaction equilibrium (due to transamidation and/ortransesterification reactions), the order in which the reactants arecombined typically does not impact on the properties of the productcopolymer.

Any catalyst that may accelerate amide and/or ester formation betweencarboxyl, amine and/or hydroxyl groups may be present in the reactionmixture described above. Thus, mineral acid such as phosphoric acid, ortin compounds such as dibutyltin oxide, may be present during thereaction. In addition, it is preferred to remove water from the reactionmixture as it is formed upon amide and, optionally, ester formation.This is preferably accomplished by maintaining a vacuum on the reactingmixture, or by passing a stream of an inert gas (e.g., nitrogen) acrossthe top of the reaction mixture.

The block copolymers of the invention may be used to thicken and/or gela liquid (where the term “a liquid” includes a mixture of liquids). Asused herein, the term liquid refers to any substance that is or can be aliquid (as opposed to a solid or gas) at a temperature between 10-60° C.Generally stated, a liquid is a fluid material where the components ofthe material are held together by intermolecular interactions, asopposed to a gas, where a gas is also fluid but the components of thegas are not held together by intermolecular interactions. A material isa “liquid” according to the present invention even though under aspecific set of conditions the material does not flow. For instance,methyl ethyl ketone (MEK), also known as 2-butanone, is a liquidaccording to the present invention even though MEK can be a solid undercertain conditions (e.g., at less than −87° C.) and can be a gas underother conditions (e.g., at greater than 80° C.). Thus, a composition ofthe present invention that includes a “liquid” does not necessarily havethat liquid in a fluid liquid state. For instance, a composition of thepresent invention that contains MEK is still a composition of thepresent invention even though the composition may be at such a lowtemperature that the liquid no longer flows, and in fact may be regardedas a solid. So long as the candidate liquid in neat form would flow at atemperature between 10-60° C., then that is a liquid according to thepresent invention.

The composition of the present invention may be a liquid, which willtypically be the case at elevated temperatures. The composition mayalternatively be a gel, which will typically be the case at roomtemperature. Even when the composition is in the gel state, as explainedabove, the polar liquid of the composition will be deemed to be a“liquid”, i.e., a fluid, so long as the polar liquid in a neat statewould be a fluid liquid at least one temperature in the range of 10-60°C. The polar liquid need not be fluid in the composition of theinvention, e.g., the composition need not, and preferably does notdemonstrate syneresis.

The liquid present in the compositions of the present invention is notonly fluid at least one temperature in the range of 10-60° C., but it isalso polar. The term polar means that the liquid contains a dipolemoment. In one aspect, the liquid contains a heteroatom, e.g., oxygen ornitrogen, in addition to one or more carbons, where the presence of theheteroatom will typically imbue the liquid with a dipole so that theliquid is a polar liquid according to the present invention. Forinstance, the polar liquid may contain one or more oxygen atoms, and bea ketone-containing liquid, an ester-containing liquid or anether-containing polar liquid. The polar liquid may contain oxygen andnitrogen atoms, e.g., the polar liquid may be an amide-containingliquid. The polar liquid may contain oxygen and sulfur atoms, e.g., thepolar liquid may be a sulfoxide-containing liquid.

In a preferred embodiment, the polar liquid or surfactant forms a gelupon being combined with a block copolymer of the present invention. Asused herein, the term “a”, as in the term “a polar liquid” refers to oneor more of the indicated items. For example, “a fragrance” refers to oneor more fragrance chemicals.

In one aspect, the polar liquid is an ester-containing liquid having aformula selected from R⁶—CO₂—R⁶ and R⁶—CO₂—R⁷—CO₂—R⁶ wherein R⁶ and R⁷are organic moieties having 1-12 carbons, where two R⁶ moieties in aliquid may be joined together to provide a lactone, and a R⁶ and R⁷moiety in a liquid may be joined together to form a lactone. Forexample, R⁶ may be selected from C₁-C₁₂ alkyl, C₁-C₁₂hydroxy-substituted alkyl, C₁-C₁₂ alkoxy-substituted C₁-C₁₂ alkyl,C₆-C₁₂ aryl-substituted C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₁-C₁₂hydroxyalkenyl, C₁-C₁₂ alkoxy-substituted C₁-C₁₂ alkenyl, C₈-C₁₂ aryl,C₁-C₁₂ alkyl-substituted C₆-C₁₂ aryl, C₆-C₁₂ hydroxy-substituted aryl,C₆-C₁₂ alkoxy-substituted C₆-C₁₂ aryl; and R⁷ may be selected fromC₁-C₁₂ alkylene, C₁-C₁₂ hydroxy-substituted alkylene, C₂-C₁₂ alkenylene,C₆-C₁₂ arylene, C₆-C₁₂ hydroxy-substituted arylene, C₁-C₁₂alkoxy-substituted C₆-C₁₂ arylene. As another example, theester-containing liquid may be selected from the group consisting ofethyl lactate, butyl propionate, dibutyl adipate, ethoxyethylpropionate, butyl acrylate, vinyl propionate, butyl acetate, dibutylsebacate, diethylphthalate, vinyl acetate, methyl methacrylate, ethylacetate, ethyl hexyl acetate, and gamma-butyrolactone.

In another aspect, the polar liquid is an aromatic liquid. For example,the aromatic liquid may be selected from the group consisting ofbenzene, toluene, o-xylene, m-xylene, p-xylene, styrene, alpha-methylstyrene, (C₁-C₁₈alkyl)-benzoate, (C₁-C₁₈ alkyl)salicylate, and (C₁-C₁₂alkyl)(C₁-C₁₂ alkyl)phthalate.

In another aspect, the polar liquid is a polar aprotic liquid. Forexample, the polar aprotic liquid may be selected from the groupconsisting of N-methylpyrrolidinone, propylene carbonate,tetrahydrofuran, dimethyl sulfoxide, methylene chloride, anddichloroethane.

In another aspect, the polar liquid is a ketone-containing liquid. Forexample, the ketone-containing liquid may have the formula R⁶—C(═O)—R⁶wherein R⁶ at each occurrence is independently selected from organicmoieties having 1-12 carbons, where two R⁶ moieties in a liquid may bejoined together to provide a cyclic ketone. For further example, theketone-containing polar liquid may be selected from acetone, methylethyl ketone, methyl isobutyl ketone and cyclohexanone.

In another aspect, the polar liquid is a sulfoxide-containing liquid.For example, the sulfoxide-containing liquid may have the formulaR⁸—S(═O)—R⁸ and R⁸ is independently selected at each occurrence fromC₁-C₆ alkyl.

In another aspect, the polar liquid is a glycol ether. For example, thepolar liquid may be a glycol ether of the formula R⁹—[O—R¹⁰—]_(n)—OHwherein R⁹ is a C₁-C₂₂ hydrocarbon, R¹⁰ is a C₂-C₆ hydrocarbonindependently selected at each occurrence, and n is an integer selectedfrom 1, 2, 3, 4, 5 and 6. As another example, the glycol ether may beethyleneglycol mono phenyl ether, dipropyleneglycol mono methyl ether ortripropyleneglycol mono methyl ether.

Polar liquids are very well known in the art, and can be obtained frommany commercial suppliers. See, e.g., Acros Organics (Pittsburgh Pa.),Aldrich Chemical (Milwaukee Wis., including Sigma Chemical and Fluka),Apin Chemicals Ltd. (Milton Park UK), Avocado Research (LancashireU.K.), BDH Inc. (Toronto, Canada), Bionet (Cornwall, U.K.), ChemserviceInc. (West Chester Pa.), Crescent Chemical Co. (Hauppauge N.Y.), EastmanOrganic Chemicals, Eastman Kodak Company (Rochester N.Y.), FisherScientific Co. (Pittsburgh Pa.), Fisons Chemicals (Leicestershire UK),Frontier Scientific (Logan Utah), ICN Biomedicals, Inc. (Costa MesaCalif.), Key Organics (Cornwall U.K.), Lancaster Synthesis (WindhamN.H.), Maybridge Chemical Co. Ltd. (Cornwall U.K.), Parish Chemical Co.(Orem Utah), Pfaltz & Bauer, Inc. (Waterbury Conn.), Polyorganix(Houston Tex.), Pierce Chemical Co. (Rockford Ill.), Riedel de Haen AG(Hannover, Germany), Spectrum Quality Product, Inc. (New Brunswick,N.J.), TCI America (Portland Oreg.), Trans World Chemicals, Inc.(Rockville Md.), and Wako Chemicals USA, Inc. (Richmond Va.).

In another aspect, the polar liquid may include, or may exclusively be,a liquid fragrance. Liquid fragrances are well known in the art and aresold by many companies. Liquid fragrances are also known as aromachemicals. For example, the following companies sell fragrance materialsas a major part of their business: IFF (New York, N.Y., USA; seeiff.com); Givaudan (Vernier, Switzerland; see givaudan.com); Firmenich(Princeton, N.J., USA; see firmenich.com); Quest International (Naarden,The Netherlands; see quest-international.com); Takasago (Rockleigh,N.J., USA; see takasago-i.co.jp); Haarman & Reimer (Holzminden, LowerSaxony, Germany; see haarmann-reimer.com); Dragoco (Holzminden, LowerSaxony, Germany; see dragoco.com); T. Hasegawa Co., Ltd. (Tokyo, Japan;see t-hasegawa.co.jp); Mane SA (Bar-sur-Loup, France; see mane.com);Aldrich-Sigma Flavors and Fragrances, a group within Aldrich ChemicalCo., Inc. (Milwaukee, Wis., USA: see sigma-aldrich.com/safc).

Fragrance chemicals may be classified based upon their common functionalgroups. For examples, acetylenes, alcohols, aldehydes, amines, aminoacids, carboxylic acids, essential oils, ester/lactones, ethers/acetals,heterocycles, hydrocarbons, ketones, nitrites, olefins (includingcumulated double bonds), and sulfur compounds (sulfides, disulfides andmercaptans) are classes of fragrance chemicals. Fragrance chemicals mayalso be classified based on their common smell. For example, aliaceous,animal, balsamic, camphoraceous, citrus, coffee, earthy, ethereal,floral, fruity, green, herbaceous, meaty, medicinal, minty, mossy,musty, nutty, pepper, smoky, soapy, spicy, sulfurous, vegetable, waxy,wine-like and woody are some common smells that are recognized by thearoma chemist. These classes of fragrance chemicals represent fragrancechemicals according to the present invention. Essential oils, which arenaturally-derived fragrance chemicals, are also liquid fragrancesaccording to the present invention.

The combination of a resin composition comprising a block copolymer ofthe formula hydrocarbon-polyether-polyamide-polyether-hydrocarbon, and aliquid fragrance chemical, can be utilized as a fragrance-emittingarticle. Fragrance-emitting articles are well known as a desirablematerial of commerce. In order to formulate a fragrance-emitting articlefrom a resin composition comprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon according to thepresent invention, blends of liquid fragrance and resin may be preparedat various weight ratios, e.g., 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,and 90% by weight of liquid fragrance in a combination of liquidfragrance and resin. These blends may be heated to provide a homogeneouscomposition, and then cooled to provide the fragrance-emitting article.The formulator will be able to select from these formulations a suitableformulation that meets the needs of consistency and fragrance-releasecharacteristics for the desired end-use. When gel-like consistencies arecreated, the gel may be molded into various shapes. Other components maybe added to the compositions, to provide desirable end-use properties inaddition to fragrance release.

In another aspect, the polar liquid may include, or may exclusively be,a liquid polyepoxy resin. Although liquid polyepoxy resins are wellknown in the art, some salient features of liquid polyepoxy resins willbe described. In general, liquid polyepoxy resins are any liquid organiccompound having at least two oxirane rings, where oxirane rings are alsoknown as epoxy groups. In addition to the epoxy groups, the polyepoxyresin will contain aliphatic, alicyclic, heterocyclic, cycloaliphatic,and/or aromatic groups, in addition to combinations thereof. Thepolyepoxides may be linear polymers having terminal epoxy groups (forexample, a diglycidyl ether of a polyoxyalkylene glycol), polymershaving skeletal oxirane units (for example, polybutadiene polyepoxide),or polymers having pendent epoxy groups (for example, a glycidylmethacrylate polymer or copolymer). The molecular weight of the liquidpolyepoxy resin may vary from about 10² to about 10⁵ or more. Mixturesof various epoxy resins can also be used in the hot melt compositions ofthe invention.

Liquid polyepoxy resins are frequently described in the patent, journaland trade literature. See, e.g., U.S. Pat. No. 3,117,099 and U.S. Pat.No. 3,018,262. Specific exemplary polyepoxy resins include halogenatedepoxy resins, 1,4-butanediol diglycidyl ether (for example, ARALDITERD-2™ from Ciba-Geigy Corp.), diglycidyl ethers of Bisphenol A (forexample, EPON 828™, EPON 1004™, and EPON 1001F™ from ResolutionPerformance Products, Inc. (Houston, Tex., formerly the Resins &Versatics business of Shell Chemicals); and DER-332™ and DER-334™ fromDow Chemical Co., Midland, Mich.), diglycidyl ether of Bisphenol F (forexample, ARALDITE GY281™ from Ciba-Geigy Corp., Hawthorne, N.Y., andEPON 862™ from Resoultion Performance Products, Inc.),3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexene carboxylate (forexample, ERL-4221 ™ from Dow Chemical Company), vinylcyclohexene dioxide(for example, ERL 4206™ from Dow Chemical Co.), bis(3,4-epoxycyclohexyl)adipate (for example, ERL-4299™ from Dow Chemical Co), dipentene dioxide(for example, ERL-4269™ from Dow Chemical Company), epoxidizedpolybutadiene (for example, OXIRON 2001 ™ from FMC Corp.),2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane (forexample, ERL-4234™ from Dow Chemical Company), epoxy silanes, forexample, beta-3,4-epoxycyclohexyl-ethyltrimethoxysilane andgamma-glycidoxypropyltrimethoxysilane, hydrogenated bisphenolA-epichlorohydrin based epoxy resins (for example EPONEX 1510™ fromResolution Performance Products, Inc.), and polyglycidyl ethers ofphenol-formaldehyde novolaks (for example, DEN-431™ and DEN-438™ fromDow Chemical Co.).

The combination of a resin composition comprising a block copolymer ofthe formula hydrocarbon-polyether-polyamide-polyether-hydrocarbon, and aliquid polyepoxy resin, can be utilized in, e.g., preparing structuralmaterials. Polyepoxides can be cured by various materials well known inthe art, e.g., amines, to form a crosslinked structure. Thiscrosslinking structure can take may shapes, e.g., a film. The film maybe used as a top coat for a coated substrate, where the film provideseffective barrier properties that allows the coated substrate to retaindesirable properties for longer periods of time. Cured epoxy resin mayalso be used as an adhesive composition. The addition of the resincomposition comprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon with the polyepoxyresin according to the present invention does not preclude the polyepoxyresin from being utilized in those applications to which the polyepoxyresin would be used in the absence of the resin composition comprising ablock copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon.

In order to determine a proper formulation of resin compositioncomprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon and liquid epoxyresin, the two components may be combined in various weight ratios. Forexample, blends of liquid polyepoxy resin and block copolymer-containingcomposition may be prepared at various weight ratios, e.g., 5%, 10%,20%, 30%, 40%, 50%, 60%, 70%, 80%, and 90% by weight of liquid polyepoxyresin in a combination of polyepoxy resin and block copolymer-containingresin. These blends may be heated to provide a homogeneous composition,and then cooled to room temperature. The formulator will be able toselect from these formulations a suitable formulation that meets theneeds of consistency and reactivity with curing agents, for the desiredend-use. When gel-like consistencies are created, the gel may be moldedinto various shapes. Other components may be added to the compositions,to provide desirable end-use properties in addition to structural andadhesive properties.

In another aspect, the resin composition as described herein may becombined with a surfactant, preferably a liquid surfactant. The term“surfactant” includes soaps and detergents. Surfactants are a very wellknown class of material, and they need not be defined herein. Many ofthe above-listed suppliers of commercial chemicals will also sellsurfactants. However, it will be noted that many surfactants may beclassified based on their ionic nature, that is, into the classes ofanionic, cationic, zwiterionic, and non-ionic. Each of these surfactanttypes may be included within a composition according to the presentinvention.

Exemplary nonioinic surfactants that may be used in the compositions ofthe present invention include, without limitation, surfactantscontaining an ester bond, such as glycol esters of fatty acids, glycerolesters of fatty acids, polyglycerol esters of fatty acids, tetritol,pentitol and hexitol esters of fatty acids, polyethylene glycol estersof fatty acids, sucrose esters of fatty acids, sucrose esters oftriglycerides, sorbitan esters of fatty acids and polyoxy-ethylenatedsorbitan esters or polysorbates. The nonionic surfactant may contain anether bond, such as polyoxyethylene glycol alkylphenyl ethers andpolyoxyethylene glycol fatty alkyl ethers. The nonionic surfactant maycontain an amide bond, e.g., polyoxyethylenated alkylamides and alkyleneoxide copolymers. Of the various classes of surfactants, nonionics are apreferred surfactant for incorporation into the compositions of thepresent invention because many nonionics are liquid, while cationic andanionic tend to be solids.

Exemplary cationic or zwitterionic surfactants include betaines such asdecyl betaine, lauryl betaine, lauramidopropyl betaine, myristylbetaine, myristamidopropyl betaine, coco-betaine, cocoamidoethylbetaine, cocoamido-propyl betaine, cetyl betaine, palmamidopropylbetaine, palmitamidopropyl betaine, ricinoleamidopropyl betaine,stearamidopropyl betaine, stearyl betaine, oleyl betaine, oleamidopropylbetaine, and behenyl betaine. Another cationic or zwitterionicsurfactant class is the sultaines, where exemplary sultaineds are laurylsultaine, lauryl hydroxysultaine, coco-sultaine, coco-hydroxysultaine,cocoamido-propyl hydroxysultaine and oleamidopropyl hydroxysultaine.Alkyltrimethyl-ammonium salts are an exemplary cationic type ofsurfactant, where representative examples includedodecyltrimethylammonium bromide or chloride, cocotrimethylammoniumchloride, cetyltrimethylammonium chloride, bromide, methosulphate ortosylate, (hydrogenated) trimethylammonium tallow chloride,stearyltrimethylammonium chloride, octyldodecyltrimethylammoniumchloride, behenyltrimethylammonium chloride or methosulphate orbenzalkonium chloride, bromide or saccharinate, cetalkonium chloride,cetearalkonium bromide, lauralkonium chloride or bromide, stearalkoniumchloride, olealkonium chloride, behenalkonium chloride andcocoylbenzylhydroxyethylimidazolinium chloride.

Exemplary anionic surfactants include materials known as soaps, andinclude carboxylate and sulfonate salts, e.g., fatty acid saltsincluding sodium or potassium or other suitable counterion.

In order to determine a proper formulation of resin compositioncomprising a block copolymer of the formulahydrocarbon-polyether-polyamide-polyether-hydrocarbon and surfactant,the two components may be combined in various weight ratios. Forexample, blends of surfactant and block copolymer-containing compositionmay be prepared at various weight ratios, e.g., 5%, 10%, 20%, 30%, 40%,50%, 60%, 70%, 80%, and 90% by weight of surfactant in a combination ofsurfactant and block copolymer-containing resin. These blends may beheated to provide a homogeneous composition, and then cooled to roomtemperature. The formulator will be able to select from theseformulations a suitable formulation that meets the needs of consistencyand surfactancy. When gel-like consistencies are created, the gel may bemolded into various shapes. Other components may be added to thecompositions, to provide desirable end-use properties in addition tosurfactancy properties. These compositions may be used in, for example,cosmetics and cleaning compositions.

The block copolymer and polar liquid may be combined so as to provide amixture that has a gel-like consistency. In general, materials that havea gel-like character will maintain their shape when undisturbed but flowupon being rubbed. Gels prepared with block copolymers of the presentinvention may be anywhere from soft to hard, where a “hard” gel has arigid structure and is very resistant to deformation, while a “soft” gelexhibits some, but not too much, resistance to deformation. Anillustration of “soft” gel may be seen in the preparation of Jell-O®dessert, which is a well known food product from Kraft Foods Inc.(division of Philip Morris Companies Inc., Northfield, Ill.). Whenprepared according to the package instructions, Jell-O® dessert is mixedwith water to form a relatively soft gel. A gellant may be distinguishedfrom a Theological additive, where a Theological additive increases theshear thinning of a polar liquid/additive combination, while a gellantimparts a solid phase to the polar liquid/gellant combination. In oneaspect of the invention, the block copolymer of the present invention isnot a rheological additive. In one aspect, the present inventionprovides a gel comprising the block copolymer of the present inventionand a suitable polar liquid.

The polar liquid is a liquid at room temperature or slightly above roomtemperature. A preferred polar liquid is a polar solvent, whereexemplary polar solvents include lower alcohols (e.g., methanol,ethanol, propanol, butanol), glycols, ethers, glycol ethers (i.e.,polyalkyleneglycol ethers), and polyols. The polar solvent may be amixture of solvents. Exemplary polar solvents are described in TABLE E(TABLE E—POLAR LIQUIDS CONTAINING HYDROXYL AND/OR ETHERFUNCTIONALITIES). DOWANOL™ E-200 and E-300 are two exemplarypolyethylene glycols from the DOWANOL™ family of glycol ethers from Dow(Midland, Mich.; @dow.com) while DESMOPHEN™ 550 U and 1600 U arepolyether polyols from the DESMOPHEN™ family of products from BayerCorporation (Pittsburgh, Pa.; @bayer.com).

TABLE E Polar Liquids Containing Hydroxyl and/or Ether FunctionalitiesName CAS Structure Functionality Hexylene glycol 107-41-5CH₃CH(OH)CH₂C(CH₃)₂OH 1 secondary OH (a.k.a. 2-methyl-2,4- 1 tertiary OHpentandiol) Propylene glycol 57-55-6 CH₃CH(OH)CH₂OH 1 primary OH (a.k.a.1,2-propanediol) 1 secondary OH Ethylene glycol 107-21-1 HOCH₂CH₂OH 2primary OH Di(propylene glycol) 25265-71-8 HOC₃H₆OC₃H₆OH 2 primary OH'sMixture of 1,2 and 1,3 2 secondary OH's isomers 1/1 prim/sec OH 1 etherDi(ethylene glycol) 111-90-0 C₂H₅OCH₂CH₂OCH₂CH₂OH 2 ether ethyl ether 1prim. OH Diethylene glycol 111-96-6 CH₃OCH₂CH₂OCH₂CH₂OCH₃ 3 etherdimethyl ether (a.k.a. 2-methoxyethyl ether) DOWANOL ™ E-200 25322-68-3H(OCH₂CH₂)_(n)OH 2 prim. OH Poly(ethylene glycol) ~4 ether MW = 200DOWANOL ™ E-300 25322-68-3 H(OCH₂CH₂)_(n)OH 2 prim. OH Poly(ethyleneglycol) ~6 ether MW = 300 DESMOPHEN ™ 1600 U 25322-69-4 NOT KNOWN NOTKNOWN Linear polyether polyol DESMOPHEN ™ 550 U 25723-16-4 NOT KNOWN NOTKNOWN Branched polyether polyol Poly(ethylene glycol) 24991-55-7CH₃(OCH₂CH₂)_(n)OCH₃ ~6 ether dimethyl ether MW = 250

In one aspect, the polar liquid is a liquid that contains ether and/orhydroxyl groups. In one aspect of the invention, the polar liquid isDMSO, i.e., dimethylsulfoxide. The liquid may contain more than onecomponent, e.g., ether as well as hydroxyl-containing material. In themixture, the gellant (block copolymer) typically contributes 10-95%, andthe polar liquid typically contributes 5-90%, of the combined weight ofthe gellant and the polar liquid. Preferably, the gellant is combinedwith the polar liquid such that the weight percent of gellant in thegellant+polar liquid mixture is about 5-50%, and preferably is about10-45%. Such mixtures are preferably gels, where the gels may betransparent, translucent or opaque, depending on the precise identitiesof the gellant and polar liquid, as well as the concentration of gellantin the mixture.

In order to prepare a gel from a polar liquid and block copolymer, thetwo components are mixed together and heated until homogeneous. Atemperature within the range of about 80-150° C. is typically sufficientto allow the block copolymer to completely dissolve in the polar liquid.A lower temperature may be used if a solution can be prepared at thelower temperature. Upon cooling, the mixture forms the gelledcomposition of the invention. Optional components may be added to themolten composition, and are dispersed and/or dissolved to provide ahomogeneous composition prior to cooling of the molten composition.

In another embodiment, the block copolymer-containing gels of thepresent invention may be formulated such that they are transparent.There are various degrees of transparency, ranging from “crystal” clearto hazy, which may be achieved with gels of the invention. In order toprovide some measure of the absolute transparency of a gel, thefollowing test has been devised. A white light is shined through a gelsample of a given thickness at room temperature, and the diffusetransmittance and the total transmittance of the light are determined.The percent haze for a sample is determined by the equation: %haze=(diffuse transmittance/total transmittance)×100. Samples areprepared by melting the gel (or product made therefrom) and pouring themelt into 50 mm diameter molds. The samples may be prepared at twothicknesses, e.g., 5.5±0.4 mm and 2.3±0.2 mm.

Clarity measurements may be made on a Hunter Lab Ultrascan SphereSpectrocolorimeter using the following settings: specular included, UVoff, large area of view, illuminate D65, and observer 10°. Using thisprotocol with a 2.3 mm thickness sample, block copolymer-containing gelof the present invention may have a % haze value of less than 75, whileparaffin wax has a % haze value of over 90. The % haze value for a gelof the present invention can be increased if desired, by appropriateselection of polar liquid and gellant. Thus, the present inventionprovides gels (and articles made therefrom) having a transparency(measured by % haze) of less than 75, preferably less than 50, morepreferably less than 25, still more preferably less than 10, and yetstill more preferably of 5 or less.

In one embodiment, the gels containing block copolymer of the presentinvention are also stable, in that they do not display syneresis. Asdefined in the McGraw-Hill Dictionary of Scientific and Technical Terms(3^(rd) Edition), syneresis is the spontaneous separation of a liquidfrom a gel or colloidal suspension due to contraction of the gel.Typically, syneresis is observed as the separation of liquid from a gel,and is sometimes referred to as “bleeding”, in that wetness is seenalong the surfaces of a gel that displays syneresis. From a commercialpoint of view, syneresis is typically an undesirable property, and thegels of the present invention desirably, and surprisingly do not exhibitsyneresis. In one embodiment, the gels of the invention, and articlesprepared therefrom, may be stable in the sense that they do not exhibitsyneresis. Thus, they do not have an oily feeling when handled.

A gel formed from a block copolymer and the present invention may beused to prepare an antiperspirant or deodorant. The antiperspirant mayalso contain one or more of aluminum chlorohydrate, aluminum-zirconiumtetrachlorohydrate, aluminum-zirconium polychlorohydrate complexed withglycine, and aluminum-zirconium complexed with any of trichlorohydrate,octachlorohydrate, and sesquichlorohydrate. The gels, and the formulatedantiperspirant, are preferably transparent.

The block copolymer-containing gels of the invention may be (althoughneed not be) essentially transparent. When transparent, the gels may becombined with colorants (as well as other ingredients) to form lipstickor other cosmetic products, without the gel interfering with or taintingthe appearance of the colorant. The gels of the present invention may becombined with aluminum zirconium salts, as well as other ingredients, toform colorless underarm deodorant/antiperspirant, which is currentlyquite popular. The gels of the invention are also useful in otherpersonal care products, e.g., cosmetics such as eye make-up, lipstick,foundation make-up, costume make-up, as well as baby oil, make-upremovers, bath oil, skin moisturizers, sun care products, lip balm,waterless hand cleaner, medicated ointments, ethnic hair care products,perfume, cologne, oral care bases (e.g., for toothpaste) andsuppositories.

In addition, the gels of the present invention may be used in householdproducts such as air fresheners, decorative table-top food warmers(i.e., they may be burned slowly to heat, e.g., an overhead chafingdish), automobile wax/polish, candles, furniture polish, metalcleaners/polishes, household cleaners, paint strippers and insecticidecarriers.

Formulations to prepare such materials are well known in the art. Forexample, U.S. Pat. Nos. 3,615,289 and 3,645,705 describe the formulationof candles. U.S. Pat. Nos. 3,148,125 and 5,538,718 describe theformulation of lipstick and other cosmetic sticks. U.S. Pat. Nos.4,275,054, 4,937,069, 5,069,897, 5,102,656 and 5,500,209 each describethe formulation of deodorant and/or antiperspirant.

The block copolymer of the invention may be incorporated into commercialproducts such as those listed above, as well as cable filling compounds,urethane/alkyl paint additives, and soaps/surfactants. These productsmay be prepared by blending the block copolymer with the othercomponents of the product. In these commercial products, the blockcopolymer will typically be present at a concentration of about 1% toabout 50% of the composition, based on the total weight of thecomposition. It is a routine matter to optimize the amount of blockcopolymer in a composition, and indeed the amount will vary depending onthe actual product and the desired consistency of the product. Ingeneral, as more block copolymer is used in a formulation, the productwill display a more pronounced gel character, and will form a morerigid, or hard, gel.

The following examples are offered by way of illustration and not by wayof limitation.

EXAMPLES

In the following Examples, softening point was measured using a ModelFP83HT Dropping Point Cell from Mettler Instruments, Mettler-ToledoInternational, Inc. (CH-8606 Greifensee, Switzerland; @mt.com), with aheating rate of 1.5° C./min. Techniques to measure acid and aminenumbers are well known in the art and need not be described here. See,e.g., ASTM D-465 (1982) from American Society for Testing and Materials(West Conshohocken, Pa.; @astm.org).

EMPOL™ dimer acid was obtained from Henkel Company, and is now availablefrom Cognis (@cognis.com). Ethylene diamine (EDA) is available fromAldrich (Milwaukee, Wis.; @sigma-aldrich.com). NEODOL™ alcoholethoxylates are available from Shell Chemical Company (Houston, Tex.;@shell.com).

Example 1 Hydrocarbyl Ethoxylate-Terminated Block Copolymer

A mixture of 67.4 parts EMPOL™ 1008 dimer acid (100 eq. % of acidequivalents), 5.1 parts ethylene diamine (EDA) (72.2 eq. % ofamine+hydroxyl equivalents, based on acid equivalents) and 27.4 partsNEODOL™ 23-6.5 alcohol ethoxylate (27.4 eq. % of amine+hydroxylequivalents, based on acid equivalents) was prepared and heated to about200-250° C. under a nitrogen atmosphere with simultaneous removal ofwater. A small amount (ca. 0.1-1.0 parts) hypophosphorous acid was addedto minimize coloration of the product. Progress of the reaction wasmonitored by periodically pulling samples and measuring the acid and/oramine number of the product mixture. A nitrogen sparge was introduced toreduce the amine number to a desired level. The product block copolymerwas characterized and found to have an acid number of 18.3 (higher thanthe theoretical value of 6, indicating incomplete reaction of thealcohol ethoxylate), an amine number of 1.1, a softening point of 90.3°C. and a viscosity at 160° C. of 85 cPs.

Example 2 Hydrocarbyl Ethoxylate-Terminated Block Copolymer

The procedure of Example 1 was followed using 57.6 parts EMPOL™ 1008(100 eq. % acid), 4.4 parts EDA (71.7 eq. % amine+hydroxyl, based onacid equivalents) and 38.0 parts NEODOL™ 45-13 (23.9 eq. %amine+hydroxyl, based on acid equivalents). The product had an acidnumber of 16.9 (higher than the theoretical value of 6, indicatingincomplete reaction of the alcohol ethoxylate), an amine number of 0.6,a softening point of 92° C. and a viscosity at 160° C. of 94 cPs. Thesoftening point is approximately the same as the block copolymer ofExample 1, indicating that ethoxylate molecular weight does not have alarge impact on softening point. The gelling behavior of this blockcopolymer is described in Example 4.

Example 3 Hydrocarbyl Ethoxylate-Terminated Block Copolymer

The procedure of Example 1 was followed using 47.8 parts EMPOL™ 1008(100 eq. % acid), 2.8 parts EDA (56.2 eq. % amine+hydroxyl, based onacid equivalents) and 49.4 parts NEODOL™ 45-13 (37.4 eq. %amine+hydroxyl, based on acid equivalents). The product had an acidnumber of 21.4 (higher than the theoretical value of 6, indicatingincomplete reaction of the alcohol ethoxylate), an amine number of 0.4,a softening point of 83.7° C. and a viscosity at 160° C. of 67 cPs. Thesoftening point and melt viscosity are both lower than that of thecopolymer of Example 2, indicating that a higher degree of terminationreduces the molecular weight of the block copolymer. The gellingbehavior of this block copolymer is described in Example 4.

Example 4 Gelling Behavior of Hydrocarbyl Ethoxylate-Terminated BlockCopolymer

The copolymers of Examples 2 and 3 were combined with various polarliquids at a 15 wt % copolymer concentration. The observed gellingproperties of the hydrocarbyl-ethoxylate-terminated polyamides aredescribed in TABLE F (TABLE F—GELATION PROPERTIES OFETHOXYLATE-POLYAMIDES COPOLYMERS AT 15% RESIN). The gelling behaviorindicates that the higher level of ethoxylate termination (Example 3)makes the resin more compatible with the polar liquids. This isdemonstrated by the fact that the copolymer of Example 2 gels hexyleneglycol to form a clear gel, 2-methoxyethyl ether to form an opaque gel,and forms two phases in dipropylene glycol; while the copolymer ofExample 3 dissolves in hexylene glycol, forms a clear gel inmethoxyethyl ether, and forms an opaque liquid in dipropylene glycol.This indicates that the gelling ability of these resins is a balancebetween their compatibility (ethoxylate content) and amide content(where amide content is directly proportional to the molecular weight ofthe resin). However, neither of the copolymers of Examples 2 or 3 wascapable of gelling propylene glycol, polyethylene glycol, dipropyleneglycol. This may be due to the hydrophobic alkyl chain within theethoxylate molecule. In TABLE F, and elsewhere in the TABLES set forthherein, “ND” indicates “not determined”.

TABLE F Gelation Properties of Ethoxylate-Polyamide Copolymers at 15%Resin Polar Liquid Example 2 Example 3 Hexylene glycol Transl. Gel Clearliquid Propylene glycol 2 phases 2 phases Polyethylene glycol (E-200) 2phases 2 phases Poly(ethylene glycol) dimethyl ether Opaque gel Opaquegel Diethylene glycol ethyl ether Opaque gel N/D Dipropylene glycol 2phases Opaque liquid 2-Methoxyethyl ether Opaque gel Clear gel

Example 5 Hydrocarbyl Polyalkyl Glycol-Terminated Block Copolymer

The procedure of Example 1 was followed using 61.8 parts EMPOL™ 1008(100 eq. % acid), 4.3 parts EDA (66.5 eq. % amine+hydroxyl, based onacid equivalents) and 33.9 parts MPEG 550 (28.5 eq. % amine+hydroxyl,based on acid equivalents). The product had an acid number of 20.5(higher than the theoretical value of 6, indicating incomplete reactionof the alcohol ethoxylate), an amine number of 1.0, a softening point of91° C. and a viscosity at 160° C. of 52 cPs. The gelling behavior ofthis block copolymer is described in Example 8. At high terminationlevels (see Examples 6 and 7), the properties of the block copolymer aredominated by the polyalkyl glycol.

Example 6 Hydrocarbyl Polyalkyl Glycol-Terminated Block Copolymer

The procedure of Example 1 was followed using 37.3 parts EMPOL™ 1008(100 eq. % acid), 2.7 parts EDA (68.9 eq. % amine+hydroxyl, based onacid equivalents) and 59.9 parts MPEG 2000 (23.0 eq. % amine+hydroxyl,based on acid equivalents). The product had an acid number of 17.1(higher than the theoretical value of 6, indicating incomplete reactionof the alcohol ethoxylate), an amine number of 0.4, a softening point of75.4° C. and a viscosity at 160° C. of 224 cPs. The gelling behavior ofthis block copolymer is described in Example 8.

Example 7 Hydrocarbyl Polyalkyl Glycol-Terminated Block Copolymer

The procedure of Example 1 was followed using 26.1 parts EMPOL™ 1008(100 eq. % acid), 1.6 parts EDA (56.5 eq. % amine+hydroxyl, based onacid equivalents) and 31.8 parts MBPPG 2500 (31.8 eq. % amine+hydroxyl,based on acid equivalents). The product had an acid number of 17.3(higher than the theoretical value of 6, indicating incomplete reactionof the alcohol ethoxylate), an amine number of 0.5, a softening point of41.9° C. and a viscosity at 160° C. of 35 cPs. The gelling behavior ofthis block copolymer is described in Example 8.

Example 8 Gelling Behavior of Hydrocarbyl Ethoxylate-Terminated BlockCopolymer

The copolymers of Examples 5, 6 and 7 were combined with various polarliquids at a 15 wt % copolymer concentration. The observed gellingcharacteristics of these copolymers is given in TABLE G (TABLEG—GELATION PROPERTIES OF POLYALKYL GLYCOL-POLYAMIDE COPOLYMERS AT 15%RESIN). The copolymers of Examples 5 and 6 gelled hexylene glycol, butthe copolymer of Example 6 gave an opaque gel. The opaque gel is likelycaused by the MPEG 2000, which dissolves in hexylene glycol at elevatedtemperature, but crystallizes out when cooled. This result suggests thatthe terminal molecule is preferably a liquid that is soluble in theglycol, if a transparent gel is desired. The copolymer of Example 5gelled the various polar liquids with combinations of hydroxyl and etherfunctionality, but was incompatible with polyethylene glycol andpropylene glycol. This result suggests that the level of liquidterminator is desirably high in some instances.

However, at >70 wt % of a liquid terminator, the copolymer of Example 7was a very soft opaque solid that was incompatible with propyleneglycol. This behavior may be due to unreacted dimer in the resin that isincompatible with the glycol. Thus, the hydrocarbon-terminated polyalkylglycol-polyamide block copolymers have excellent gelling properties whena liquid terminator is used and the level of termination is not toogreat. As with the hydrocarbon-terminated ethoxylate-polyamidecopolymers, the gelling characteristics of these resins is a balancebetween the amide density and polyalkyl glycol content.

TABLE G Gelation Properties of Polyalkyl Glycol-Polyamide Copolymers at15% Resin Polar Liquid Example 5 Example 6 Example 7 Hexylene glycolClear gel Opaque gel ND Propylene glycol 2 phases 2 phases 2 phasesPolyethylene glycol 2 phases 2 phases ND (E-200) Diethylene glycolTransl. gel ND ND ethyl ether Poly(ethylene glycol) Opaque gel ND NDdimethyl ether 2-Methoxyethyl ether Transl. gel ND ND Dipropylene glycolOpaque gel ND ND

Example 9 Hydrocarbyl Oxa Acid-Terminated Block Copolymer

The procedure of Example 1 was followed using 74.4 parts EMPOL™ 1008 (75eq. % acid, based on total acids), 15.7 3,6,9-trioxadecanoic acid (25eq. % based on total acids) and 9.9 parts EDA (94.7 eq. % amine, basedon acid equivalents). The product had an acid number of 11.6, an aminenumber of 1.1, a softening point of 88.1° C. and a viscosity at 183° C.of 35 cPs. The use of an oxa acid tends to provide a darker coloredblock copolymer, relative to the use of polyalkyl glycols and alcoholethoxylates. The gelling behavior of this block copolymer is describedin TABLE H below.

TABLE H Gelation Properties of Oxa Acid-Polyamide Copolymer at 15% ResinPolar Liquid Gel Description 15% in hexylene glycol Clear gel 15% inPropylene glycol 2 phases 15% in polyethylene glycol (E-200) 2 phases15% in diethylene glycol ethyl ether Transl. Gel 15% in dipropyleneglycol Opaque gel 15% in poly(ethylene glycol) dimethyl ether opaqueliquid 15% in 2-methoxyethyl ether Opaque gel

Examples 10-18 Hydrocarbyl Polyoxyalkyleneeamine-Polyamide BlockCopolymer

The procedure of Example 1 was followed using EMPOL™ 1008, UNIDYME 18dimer acid (from Arizona Chemical, Jacksonville, Fla.), EDA,hexamethylene diamine (HMDA, Aldrich), sebacic acid (sebacic, Aldrich),polyoxyalkyleneamine, etc. in the amounts shown in TABLE I. TABLE I alsoprovides the acid number (AN), amine number (AM), softening point in °C. (s.p. (° C.), molecular weight as determined by gel permeationchromatography using THF as the polar liquid and reported as both Mn andMw by reference to polystyrene standards, and viscosity as measured incentipoise at 160° C. (Visc. @ 160° C. (cPs)) for the correspondingproduct.

Unlike the polyalkyl glycol-polyamide block copolymers, the reactantsused to prepare the polyoxyalkyleneamine-polyamide block copolymersreact almost completely with the terminator (theoretical acid number=6).Increasing the level of termination (Examples 14 and 13) resulted in alower softening point and viscosity. The addition of HMDA lowers thesoftening point (Examples 13 and 17) relative to the use of EDA only,while the addition of sebacic acid as a co-diacid raised the softeningpoint.

The diglycol amine polymer (Example 18) was made by reacting at 180° C.without vacuum in order to only react the amine and not the hydroxylgroup. This material was made to determine the effect of free hydroxylon the gelling characteristics.

The MW of the copolymers as determined by GPC indicates that thecopolymers that contain JEFFAMINE™ M-2070 amine have number average MW's(M_(n)) of 4000 to 5000. This result indicates that these resinsprimarily comprise copolymers having either two or four amide groups,i.e., the resin is primarily a mixture of bis-amide and tetra-amide.

The gelling behavior of this group of block copolymers is described inTABLE J (TABLE J—GELATION PROPERTIES OF POLYOXYALKYLENE-AMINE-POLYAMIDECOPOLYMERS AT 15% RESIN). The copolymers terminated with high levelsof >65 wt % M-2070 formed clear or transparent gels in all of theglycols, ethers, and polyols except hexylene glycol, where theydissolved. The addition of sebacic acid raised the softening point ofthe copolymer, but appeared to make the gels in propylene glycol feelsofter. Decreasing the amount of termination (i.e., increasing theaverage molecular weight (MW) of the resin) resulted in firmer gels inpropylene glycol, but the gels were transparent rather than clear. Theuse of HMDA versus EDA increased the hardness of the gels in propyleneglycol. Thus, the clearest and hardest gels are obtained by using HMDAand the maximum level of termination possible.

Generally, the gel characteristics are related to the level oftermination and the density of amide groups. The use of HMDA versus EDAincreased the hardness of the gels in propylene glycol. Thus, theclearest and hardest gels are obtained by using HMDA and the maximumlevel of termination possible. Resins having high levels of M-2070 wereslightly soluble in water (at concentrations up to about 3-4%). Thus,these resins are extremely hydrophilic materials and demonstrate somesurfactant properties.

TABLE I Composition and Properties of Polyoxyalkyleneamine-PolyamidesExample s.p. MW (GPC) Visc. @ No. Composition (eq %/wt %) AN/AM (° C.)M_(n)/M_(w) 160° C. (cPs) 10 100/60.0 EMPOL ™, 66.4/4.2 EDA, 8.0/0.9 9368.5 28.5/35.8 XTJ 505 11 100/48.4 EMPOL ™, 79.6/4.1 EDA, 8.3/0.6 103.1225 14.1/47.6 XTJ 507 12 100/22.5 EMPOL ™ 1008, 44.7/1.1 EDA, 7.1/0.589.2 57.5 48.5/76.4 JEFFAMINE ™ M-2070 13 100/25.7 EMPOL ™, 47.6/1.3EDA, 8.7/0.4 89 5264/7658 59.5 40.5/73.0 JEFFAMINE ™ M-2070 14 100/30.1EMPOL ™, 57.5/1.8 EDA, 6.2/0.6 98.2 5078/7804 75 32.3/68.1 M-2070 1590/24.6 EMPOL ™, 10/1.0 sebacic, 8.0/0.3 115.5 4733/7884 63 50.6/1.5EDA, 38.2/73.0 M-2070 16 75/21.0 EMPOL ™, 25/2.5 sebacic, 6.9/0.6 140.985 50.8/1.5 EDA, 38.3/75.0 M-2070 17 100/25.5 EMPOL ™, 47.5/2.5 HMDA,8.7/0.3 83 4325/7736 108 40.5/72.1 M-2070 18 100/82.6 UNIDYME ™ 18,52.9/4.5 EDA, 9.6/2.5 62.9 2004/4572 171 43.3/12.9 diglycol amine

TABLE J Polar Liquid Example 10 Example 11 Example 13 Example 14 Example15 Example 17 Example 18 Hexylene glycol Clear gel Transl. gel Clearliq. Clear liq. Clear liq. Clear liq. Clear liq. Propylene glycol 2phases 2 phases Clear gel Transl. Gel Clear gel Clear gel 2 phasesEthylene glycol ND ND ND ND ND 2 phases ND Polyethylene glycol (E-200) 2phases 2 phases Clear gel Clear gel Clear gel Transl. Gel NDPolyethylene glycol (E-300) ND ND Clear gel Clear gel Clear gel Cleargel ND Diethylene glycol ethyl ether Clear gel ND ND ND ND ND NDDipropylene glycol Opaque gel Opaque gel Clear gel Transl. Gel ND Cleargel ND Poly(ethylene glycol) ND Transl. Gel Clear gel ND ND Clear gel NDdimethyl ether 2-methoxyethyl ether ND Transl. gel Clear gel Transl. gelND Clear gel Opaque gel DESMOPHEN ™ 1600 U ND ND Clear gel Transl. GelND ND ND Linear polyether polyol DESMOPHEN ™ 550 U ND ND Clear gel Cleargel ND ND ND Branched polyether polyol

Examples 19-22 Hydrocarbyl Polyoxyalkyleneamine-Polyamide BlockCopolymer

Four resins of the invention were prepared, essentially according to theprocedure of Example 1, having the compositions, physical properties andgelation properties as set forth in Table K (Composition and Propertiesof Poly(oxyalkylene) Monoamine Terminated Polyamides Containing NoCo-Diamine).

TABLE K Composition and Properties of Poly(oxyalkylene) MonoamineTerminated Polyamides Containing No Co-Diamine Resin Composition EMPOL1008 - Termination Co-Diamine Propylene Example M2070 - EDA Eq. % onFraction Total Glycol Cut No. (weight %) AN/AM Dimer Diamines, Eq. (20wt %) 19 22.5 - 76.3 - 1.1 2.9/0.6 47.8 0 Clear jelly 20 25.1 - 73.3 -1.6 N.D. 41.2 0 Clear gel * 21 27.1 - 71.1 - 1.8 N.D. 37.0 0 Sl. hazygel * 22 24.0 - 74.7 - 1.4 1.6/N.D. 44.0 0 Sl. hazy gel *

Examples 23-32 Hydrocarbyl Polyoxyalkyleneamine-Polyamide BlockCopolymer

A series of resins was prepared having varying amounts of ethylenediamine and polyetherdiamine (specifically XTJ-504, formerly JEFFAMINE®EDR-148). The reactants for these resins, as well as the physicalproperties and gelation properties of the resin, are set forth in TABLEL (Composition and Properties of Poly(oxyalkylene) Monoamine-terminatedPolyamides Containing JEFFAMINE® EDR-148).

These resins were prepared by heating about 100 g of the ingredients(total charge) in a 250 mL Erlenmeyer flask in the presence of threedrops of 25% aqueous hypophosphorous acid under a gentle nitrogen sweepwith stirring. After the mixture reached 220° C., it was held at thattemperature for about 3 h. All of these resins were nearly water whitein color. All of these resins are soft to one degree or another; ingeneral, the higher the polyalkyleneoxy content, the softer the resin.

TABLE L Composition and Properties of Poly(oxyalkylene)Monoamine-terminated Polyamides Containing XTJ-504 Resin CompositionEMPOL 1008 - Termi- Co-Diamine M-2070 - EDA - nation Eq. % TotalPropylene Example XTJ-504 Eq. % on Eq. Glycol Cut No. (weight %) DimerDiamines (20 wt %) 23 26.8 - 70.3 - 37.0 46.0 Clear, weak 0.9 - 2.0jelly 24 31.1 - 65.2 - 29.6 39.4 Clear jelly 1.4 - 2.2 25 35.4 - 60.4 -24.1 34.9 Clear firm gel 1.8 - 2.4 26 52.4 - 39.3 - 10.6 50.0 Sl. hazyfirm 2.4 - 6.0 gel 27 79.6 - 0 - 0 100 Incompatible 0 - 20.4 28 42.0 -52.0 - 17.5 44.8 Clear gel 2.0 - 4.0 29 82.9 - 0 - 0 68.0 Incompatible2.7 - 14.4 30 64.3 - 20.0 - 4.4 100 Incompatible 0 - 15.7 31 58.5 -30.0 - 7.2 71.3 Cloudy paste 1.6 - 9.9 32 45.3 - 46.6 - 14.5 53.4 Clearjelly 1.3 - 6.8

A preferred range of termination, using M-2070, is about 15-18 eq. %with a co-diamine level of about 45-48 eq. % (more than this results ina clear, but mobile “jelly”).

Examples 33-38 Hydrocarbyl Polyoxyalkyleneeamine-Polyamide BlockCopolymer

A series of resins was prepared having varying amounts of ethylenediamine and polyetherdiamine (specifically JEFFAMINE® D-400). Thereactants for these resins, as well as the physical properties andgelation properties of the resin, are set forth in Table M (Compositionand Properties of Poly(oxyalkylene) Monoamine-terminated PolyamidesContaining JEFFAMINE® D-400.

These resins were prepared by heating about 100 g of the specifiedingredients (total charge) in a 250 mL Erlenmeyer flask in the presenceof three drops of 25% aqueous hypophosphorous acid under a gentlenitrogen sweep with stirring. After the mixture reached 220° C., it washeld at that temperature for about 3 h. All of the resulting resins werenearly water white in color. All of these resins were soft to one degreeor another; in general, the higher the polyalkyleneoxy content, thesofter the resin.

TABLE M Composition and Properties of Poly(oxyalkylene)Monoamine-terminated Polyamides Containing JEFFAMINE ® D-400 ResinComposition EMPOL 1008 - M2070 - Termination Co-Diamine Propylene Ex.EDA - Jeff. D400 Eq. % on Fraction Total Glycol Cut No. (weight %) AN/AMDimer Diamines, Eq. (20 wt %) 33 45.3 - 46.6 - 1.3 - 6.8 —/— 16.9 36.7Clear weak gel 34 35.6 - 55.9 - 2.0 - 6.4 2.8/0.6 22.2 30.3 Clear firmgel 35 35.9 - 55.6 - 2.0 - 6.4 3.2/1.3 21.9 30.2 Clear firm gel 3659.3 - 24.7 - 4.2 - 11.9 4.5/0.8 5.9 28.1 Cloudy firm gel 37 69.8 -13.8 - 5.6 - 10.8 —/— 2.8 20.9 Incompatible 38 59.4 - 24.6 - 4.2 - 11.84.4/0.6 5.9 28.0 nd

Formulations of dimer acid, EDA, M-2070, and D-400 gel propylene glycolover a wide range of compositional space, from about 45-60 wt % dimer,47-25% monoamine, and 6-12% D-400, adjusted to have a termination levelof 6-22 eq. % with about 30-35% eq. replacement of EDA with D-400.

Such resins, and formulations to prepare such resins, are a preferredembodiment of the present invention. For instance, in one aspect, thepresent invention provides a product prepared by a process of condensingreactants comprising polyoxyalkyleneamine, polyoxyalkylenediamine anddimer acid, to provide a hydrocarbon-terminated block copolymer having anumber average molecular weight of less than 10,000. Thepolyoxyalkyleneamine may have the formulaR—O—[(R^(a)—O)_(n)—(R^(b)—O)_(m)]—R^(c)—NH₂ where(R^(a)—O)_(n)—(R^(b)—O)_(m) represents a plurality of R^(a)—O andR^(b)—O units arranged in any sequence, the sum of n and m provides amolecular weight of 1,500 to 2,500 g/mol and either m or n may be zero,R is C₁-C₆alkyl, R^(a) is —CH₂CH₂—, R^(b) is —CH(CH₃)—CH₂—, and R^(c) isselected from R^(a) and R^(b). The polyoxyalkyleneamine may have thestructure of JEFFAMINE M2070. The polyoxyalkyenediamine may have theformula H₂N—[(R^(a)—O)_(n)—(R^(b)—O)_(m)]—R^(c)—NH₂ where(R^(a)—O)_(n)—(R^(b)—O)_(m) represents a plurality of R^(a)—O andR^(b)—O units arranged in any sequence, the sum of n and m provides amolecular weight of 200 to 800 g/mol and either m or n may be zero,R^(a) is —CH₂CH₂—, R^(b) is —CH(CH₃)—CH₂—, and R^(c) is selected fromR^(a) and R^(b). The polyoxyalkylenediamine may have the structure ofJeffamine D-400. The final product is resin that preferably has an acidnumber of less than 10 and an amine number of less than 10. In apreferred embodiment, the reactants further comprise ethylene diamine,as shown in TABLE M. Thus, in one aspect, the polyoxyalkyleneaminecontributes 25-47 wt % % of the reactants, polyoxyalkylenediaminecontributes 6-12 wt % of the reactants, and dimer acid contributes 45-60wt % of the reactants. In another aspect, polyoxyalkyleneaminecontributes 25-47 wt % of the reactants, polyoxyalkylenediaminecontributes 6-12 wt % of the reactants, dimer acid contributes 45-60 wt% of the reactants, and ethylene diamine contributes 1-6 wt % of thereactants.

Examples 39-45 Hydrocarbyl Polyoxyalkyleneamine-Polyamide BlockCopolymer

A series of resins was prepared having varying amounts of ethylenediamine and polyetherdiamine (specifically HUNTSMAN XTJ-500 and/orHUNTSMAN XTJ-506). The reactants for these resins, as well as thephysical properties and gelation properties of the resin, are set forthin Table N (Composition and Properties of Poly(oxyalkylene)Monoamine-terminated Polyamides Containing HUNTSMAN XTJ-500 and/orHUNTSMAN XTJ-506.)

These resins were prepared by heating about 100 g of the specifiedreactants (total charge) in a 250 mL Erlenmeyer flask in the presence ofthree drops of 25% aqueous hypophosphorous acid under a gentle nitrogensweep with stirring. After the mixture reached 220° C., it was held atthat temperature for about 3 h. All of the resulting resins were nearlywater white in color. All of these resins were soft to one degree oranother; in general, the higher the polyalkyleneoxy content, the softerthe resin.

The resin of Example 45 represents a block copolymer of the presentinvention with a high molecular weight and viscosity that still exhibitsuseful gelation properties, although it is incompatible with propyleneglycol. It had a softening point of 96.8° C., MWw of 18,240 daltons anda viscosity at 160° C. of 2,940 cPs. It dissolves in and forms a clear,firm gel with the polar liquid ethyl lactate.

TABLE N Composition and Properties of Poly(oxyalkylene)Monoamine-terminated Polyamides Containing Huntsman XTJ-500 and/orXTJ-506 Co-Diamine Fraction Resin Termination Total Propylene Ex.Components Eq. % on Diamines, Glycol Cut No. & Composition Dimer Eq. (20wt %) Empol 1008 - M2070 - EDA - XTJ500 (wt %) 39 56.0 - 23.0 - 3.8 -5.8 30.0 Cloudy firm 17.2 gel Empol 1008 - XTJ506 - EDA - Jeff. D400 (wt%) 40 59.8 - 25.2 - 3.9 - 12.0 28.0 nd 11.1 41 42.0 - 49.3 - 2.1 - 33.529.6 Clear firm 6.6 gel 42 69.9 - 12.6 - 5.1 - 5.1 25.1 Incompatible25.0 Empol 1008 - XTJ506 - EDA - XTJ500 (wt %) 43 63.3 - 15.6 - 4.5 -7.0 25.9 Incompatible 16.6 44 73.9 - 4.2 - 6.0 - 1.6 20.3 Incompatible16.0 45 70.0 - 6.5 - 5.2 - 2.7 20.3 Incompatible 18.2

Examples 46-52 Gellant Resins

The components listed below in TABLE O were charged in the amounts shownto a 250 mL glass reactor equipped with a stirrer, thermocouple probe,nitrogen gas inlet and vapor outlet to a condenser. The reaction mixturewas heated rapidly under a gentle sweep of nitrogen to about 120-130° C.at which point stirring of the liquefied mass was begun. Heating wascontinued and water vapor began appearing in the condenser trap at about150° C. Heating was continued to bring the reaction mixture to a toptemperature of about 220° C. After about 6-7 hours at that temperature,the product was discharged and tested for acid and amine number and ring& ball softening point.

TABLE O Composition and Properties of Dimer Acid-Based Gellant ResinCompositions Example Example Example Example Example Example Example 4647 48 49 50 51 52 Component Wt. % Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %EMPOL ™ 1008 dimer acid 63.3 63.3 62.9 63.2 63.6 59.6 56.0 EthyleneDiamine 4.5 4.7 5.1 4.9 4.4 4.1 3.8 JEFFAMINE ™ M-2070 amine — 20.0 20.0— — 24.6 23.0 Huntsman XTJ-506 ™ amine 15.6 — — 20.0 21.0 — —JEFFAMINE ™ D-400 amine — 12.0 — — 12.6 11.7 — Huntsman XTJ-500 ™ amine16.6 — 12.0 12.0 — — 17.2 Softening Point 92.0 98.7 101.5 101.5 97.596.3 n.d Acid Number 5.3 4.5 2.5 5.4 10.4 5.0 n.d Amine Number 0.5 1.02.5 1.2 0.4 0.7 n.d

The gellant resins of Examples 46-52 were tested as gellants for theliquids listed in TABLE P by heating 3.0 g resin and 17.0 g liquid toabout 100° C. with stirring. In almost all cases, the mixture becamehomogeneous and clear upon heating and was then poured into a samplevial and allowed to cool completely at room temperature. The mixture wasevaluated by inverting the vial with gentle shaking. If the mixture didnot move at all it was classed as “gel”. If it moved as a mass or brokeinto smaller masses and moved, it was classed as “jelly”. In some cases,the liquid flowed freely, in which case the resin was classed as“soluble”. The clarity of the mass was also evaluated and classed as“clear” (transparent), “hazy” (translucent), or “cloudy” (essentiallyopaque). In some cases, the mass cooled into a two-phase (solid-liquid)paste and was classed as “incompatible”.

Examples 53-55 CHDA-Based Gellant Resin Compositions

The components listed below in TABLE Q were reacted as in Examples 46-52above to yield cyclohexane dicarboxylic acid (CHDA) resins Examples #53-55, which were tested at 15% resin solids as described above forgelation ability with the results given in TABLE R.

TABLE Q CHDA-Based Resin Compositions Example Example Example 53 54 55Component Wt. % Wt. % Wt. % Cyclohexane Dicarboxylic Acid 21.7 17.7 19.6JEFFAMINE ™ M-2070 amine 25.6 41.9 23.1 JEFFAMINE ™ D-400 amine 52.640.3 23.6 Huntsman XTJ-500 amine — — 33.8 Softening Point 129.6 141.9119.0 Acid Number 6.4 5.2 9.3 Amine Number 1.0 0.9 1.5

TABLE P Gelation Ability of Dimer Acid-Based Resin Compositions ResinPolar Liquid Example 46 Example 47 Example 48 Example 49 Example 50Example 51 Example 52 Butyl Acrylate — — — — — — Clear gel ButylPropionate Clear gel — — — — Clear gel Clear gel Cyclohexanone Clear gel— — — — Clear gel Clear gel Dibutyl Adipate Hard, hazy Gel Hard, hazygel Hard, hazy gel Hard, hazy gel Hard, hazy gel Slightly hazy gel Cleargel Dichloroethane — Clear gel Clear gel Clear gel Soft, clear gel —Clear gel Dimethyl Sulfoxide — Clear gel — — Incompatible — Clear gelDowanol DPM Slght hazy gel Clear gel Clear gel Soft, clear gel Soft,clear gel Clear gel Clear gel Dowanol EPH Clear jelly Soft, clear gelSoft, clear gel Soft, clear gel Weak jelly Clear jelly Clear jellyEthoxyethyl Propionate Hard, hazy gel — — — — Cloudy gel Clear gel EthylAcetate Hard, hazy gel — — — — — — Ethyl Lactate Clear gel Slighty hazygel Clear gel Soft, clear gel Soft, clear gel Clear gel Clear gel MethylEthyl Ketone Slght hazy gel — — — — — — N-Methyl Pyrolidinone SolubleSoft, clear gel Soft, clear gel Soft, clear gel Soluble Soft, clear gelClear jelly Propylene Carbonate Incompatible — — — — Incompatible Cleargel Vinyl Propionate — — — — — Slightly hazy gel Xylene Clear gel Cleargel Clear gel Soft, clear gel Weak jelly Clear gel Clear gel

TABLE R Gelation Ability of CHDA-Based Resin Compositions Test ResinPolar Liquid Example 53 Example 54 Example 55 Butyl Propionate — Cleargel Incompatible Cyclohexanone Clear jelly Weak jelly Soluble DibutylAdipate Clear gel Clear gel Clear gel Dichloroethane Soluble — —Dimethyl Sulfoxide — Soluble Soluble Dowanol DPM Clear gel Clear gel —Dowanol EPH — Soluble Soluble Dowanol TPG — — Clear gel EthoxyethylPropionate Hazy gel Clear gel Hard, hazy gel Ethyl Acetate Slght hazygel — — Ethyl Lactate Soluble Soluble Soluble Methyl Ethyl Ketone Cleargel — — N-Methyl Pyrolidinone Soluble Soluble Soluble PropyleneCarbonate Cldy gel Hazy gel Clear gel Xylene Clear paste Clear gel Weakjelly

Example 56 Gelation of Epoxy Resins

A 3% solution of Example Resin #47 was prepared in EPON™ 828 liquidepoxy resin from Resolution, Inc. (formerly marketed by Shell). Themixture, when cooled to room temperature, was a homogeneous, slightlyhazy, highly viscoetastic fluid. The starting liquid epoxy had aBrookfield viscosity of 76 cP (80° C.)/1,400 cP (40° C.) but theviscosity of the 3% resin blend was too high to be measured below about80° C. Gel formation was reversible above about 85° C.; at 90° C. thelow-shear rate Brookfield viscosity of the blend was 92 cP (at 5.6 s⁻¹)and at 85° C. increased to 1,900 cP (at 1.4 s⁻¹). Further cooling of thesample to 80° C. resulted in an increase in viscosity of the sample to7,250 cP (at 0.3 s⁻¹). These very large increases in viscosity uponcooling signal the onset of gel formation. When the sample was heatedback to 90° C., the viscosity gradually decreased (over about 30minutes) to 218 cP.

Example 57 Gelation of Epoxy Resins

A 4% solution of Example Resin #55 was prepared in EPON™ 828 liquidepoxy resin as described in Example 56. The mixture, when cooled to roomtemperature, was a homogeneous, clear, highly viscous liquid,significantly more viscous than the EPON™ 828 liquid epoxy resin itself.

Example 58 Gelation of Neat Fragrance

A 5% solution of Example Resin #47 was prepared in liquid Fragrance No.005823, a neat imitation apple essence from Bush Boake Allen (a divisionof International Fragrance and Flavors). The mixture, when cooled toroom temperature, was a homogeneous, clear jelly. At a concentration of9.5% Resin #47, the mixture became a clear gel.

All publications and patent applications mentioned in this specificationare herein incorporated by reference to the same extent as if eachindividual publication or patent application was specifically andindividually incorporated by reference. This includes, but is notlimited to, U.S. patents, U.S. patent application publications, U.S.patent applications, foreign patents, foreign patent applications andnon-patent publications referred to in this specification and/or listedin the Application Data Sheet.

It will be appreciated by those skilled in the art that changes could bemade to the embodiments described above without departing from the broadinventive concept thereof. It is understood, therefore, that thisinvention is not limited to the particular embodiments disclosed, but itis intended to cover modifications within the spirit and scope of thepresent invention as defined by the appended claims.

1. A copolymer of the formula:

wherein, independently, R¹ is C₁₋₈ a hydrocarbon radical; R² is a C₂-C₄hydrocarbon diradical; R³ is a C₂-C₅₂ hydrocarbon diradical, wherein atleast 50% of the diradicals are derived from dimer acid; R⁴ is selectedfrom C₂-C₈ hydrocarbon diradicals and polyether diradicals of theformula: —(R¹¹—O)_(g)—R¹¹—, wherein R¹¹ is a C₂-C₄ hydrocarbon diradicalindependently selected at each occurrence and g is an integer rangingfrom 2 to 50; Z is selected from O and NH; x and z are integers from 2to 100; and y is an integer equal to 1 or more that provides a copolymermolecular weight of from 2,000 to 50,000.
 2. The copolymer according toclaim 1, wherein, independently, R¹ is CH₃ and Z is NH.
 3. The copolymeraccording to claim 1, wherein y is an integer from 1 to
 10. 4. Thecopolymer according to claim 1, wherein y is an integer equal to 1 ormore that provides a copolymer number average molecular weight of from2,000 to 50,000.
 5. A composition, comprising the copolymer according toclaim 1; and at least one polar liquid.
 6. The composition according toclaim 5, comprising from 5 to 50 wt % of the copolymer.
 7. Thecomposition according to claim 5, wherein the at least one polar liquidcomprises an ester-containing liquid.
 8. The composition according toclaim 7, wherein the at least one polar liquid comprises anester-containing liquid having formula R₆—CO₂—R₆ or R₆—CO₂—R₇—CO₂—R₆,wherein R₆ and R₇ are organic moieties having from 1 to 12 carbon atoms.9. The composition according to claim 8, wherein R₆ is selected fromC₁-C₁₂ alkyl, C₁-C₁₂ hydroxy-substituted alkyl, C₁-C₁₂alkoxy-substituted C₁-C₁₂ alkyl, C₆-C₁₂ aryl-substituted C₁₋₂ alkyl,C₁₋₁₂ alkenyl, C₁₋₁₂ hydroxyalkenyl, C₁₋₁₂ alkoxy-substituted C₁-C₁₂alkenyl, C₆-C₁₂ aryl, C₁-C₁₂ alkyl-substituted C₆-C₁₂ amyl, C₆-C₁₂hydroxy-substituted aryl, and C₆-C₁₂ alkoxy-substituted C₆-C₁₂ aryl, andR₇ is selected from C₁-C₁₂ alkylene, C₁-C₁₂ hydroxy-substitutedalkylene, C₂-C₁₂ alkenylene, C₆-C₁₂ arylene, C₆-C₁₂ hydroxy-substitutedarylene, and C₁-C₁₂ alkoxy-substituted C₆-C₁₂ arylene.
 10. Thecomposition according to claim 7, wherein the ester-containing liquidcomprises at least one aromatic ester.
 11. The composition according toclaim 10, wherein the aromatic ester is at least one member selectedfrom the group consisting of a (C₁-C₁₈ alkyl)benzoate, a (C₁-C₁₈ alkyl)salicylate, and a di(C₁-C₁₂ alkyl) phthalate.
 12. The compositionaccording to claim 5, wherein the at least one polar liquid comprises atleast one member selected from the group consisting of a lower alcohol,glycol, ether, glycol ether, polyalkyleneglycol ether, and polyol. 13.The composition according to claim 5, wherein the at least one polarliquid comprises at least one member selected from the group consistingof propylene glycol, 2-methoxyethyl ether, diethylene glycol ethylether, ethylene glycol, hexylene glycol, ethylene glycol monophenylether, di(propylene glycol), di(propylene glycol) monomethyl ether,di(ethylene glycol) dimethyl ether, tripropylene glycol mono methylether, poly(ethylene glycol) and poly(propylene glycol).
 14. Thecomposition according to claim 5, wherein the at least one polar liquidcomprises from 5 to 90 wt % of at least one surfactant based upon thetotal weight of the surfactant and copolymer.
 15. The compositionaccording to claim 5, wherein the polar liquid comprises an aromaticliquid.
 16. The composition according to claim 15, wherein the aromaticliquid is at least one member selected from the group consisting of a(C₁-C₁₈ alkyl)benzoate, a (C₁-C₁₈ alkyl) salicylate, and a di(C₁-C₁₂alkyl) phthalate.
 17. A personal care product, comprising any one of thecompositions according to any one of claims 5 to 16; and a colorant. 18.An antiperspirant, comprising the copolymer according to claim 1; and atleast one member selected from the group consisting of aluminumchlorohydrate, aluminum sesquichlorohydrate, aluminum dichlorohydrate,aluminum-zirconium chlorohydrates, and aluminum-zirconiumpolychlorohydrate complexed with glycine.
 19. A lipstick, comprising thecopolymer according to claim 1; at least one polar liquid; and at leastone colorant.
 20. A sun care product, comprising the copolymer accordingto claim 1; at least one (C₁-C₁₈ alkyl) salicylate; and at least onesurfactant.
 21. The sun care product according to claim 20, furthercomprising at least one ester-containing liquid.
 22. An eye make-upproduct, foundation makeup product, or costume make-up product,comprising the copolymer according to claim 1; at least oneester-containing liquid; and at least one colorant.
 23. A wax, polish,cleaner, or stripper, comprising the copolymer according to claim 1; andat least one ester-containing liquid.
 24. A wax, polish, cleaner, orstripper, comprising the copolymer according to claim 1; and at leastone aprotic liquid.
 25. The wax, polish, cleaner, or stripper accordingto claim 24, comprising from 5 to 90 wt % of at least one aprotic liquidbased upon the total weight of the aprotic liquid and copolymer.
 26. Thewax, polish, cleaner, or stripper according to claim 25, wherein the atleast one aprotic liquid is at least one member selected from the groupconsisting of N-methyl pyrrolidinone, propylene carbonate,tetrahydrofuran, dimethyl sulfoxide, methylene chloride, anddichloroethane.
 27. A fragrance emitting article, comprising thecopolymer according to claim 1; and at least one polar liquid whereinthe polar liquid comprises at least one member selected from the groupconsisting of a liquid fragrance, an essential oil, and a fragrancechemical.
 28. The fragrance emitting article according to claim 27,comprising from 10 to 90 wt % of the at least one polar liquid basedupon the total weight of the copolymer and polar liquid.
 29. Thefragrance emitting article according to claim 27, comprising from 5 to50 wt % of the copolymer based upon the total weight of the article. 30.The fragrance emitting article according to claim 27, wherein the atleast one polar liquid further comprises at least one ester-containingliquid.
 31. The fragrance emitting article according to any one of claim27 to 30, wherein the at least one polar liquid further comprises atleast one member selected from the group consisting of a lower alcohol,glycol, ether, glycol ether, polyalkyleneglycol ether, and polyol.